JP7620024B2 - Method for manufacturing composite pattern, resin composition, method for manufacturing laminate, and method for manufacturing semiconductor device - Google Patents

Description

The present invention relates to a method for manufacturing a composite pattern, a resin composition, a method for manufacturing a laminate, and a method for manufacturing a semiconductor device.

Polyimide and polybenzoxazole are used in a variety of applications due to their excellent heat resistance and insulating properties. Examples of such applications include, but are not limited to, the use of patterns containing these resins as insulating film or sealing material materials or protective films in semiconductor devices for mounting. Patterns containing these resins are also used as base films or coverlays for flexible substrates.

For example, in the above-mentioned applications, polyimide, polybenzoxazole, and polyamideimide are used in the form of a resin composition containing a polyimide precursor, a polybenzoxazole precursor, or a polyamideimide precursor.
Such a resin composition is applied to a substrate by, for example, coating, and then, if necessary, exposed to light, developed, modified, or the like, whereby a cured product of the polyimide precursor, polybenzoxazole precursor, or polyamideimide precursor can be formed on the substrate.
The resin composition can be applied by known coating methods and can form fine patterns, patterns of complex shapes, and the like by development, and therefore has a high degree of freedom in designing the cured product, and can be said to have excellent adaptability in manufacturing. In view of the excellent adaptability in manufacturing, in addition to the high performance of polyimide, polybenzoxazole, or polyamideimide, there are increasing expectations for the industrial application and development of a method for manufacturing a cured product using a resin composition containing a polyimide precursor, a polybenzoxazole precursor, or a polyamideimide precursor.

For example, Patent Document 1 describes a substrate for a multilayer wiring board, which is characterized in that an insulating adhesive layer is formed on a bump-forming surface of a metal layer having bumps for interlayer conduction on one side thereof, by applying an adhesive insulating resin material to the area excluding the bump tops, thereby forming an insulating adhesive layer in which the tops of the bumps are exposed or protrude.
Patent Document 2 describes a method for manufacturing a semiconductor device, including providing a temporary carrier, mounting a semiconductor die on the temporary carrier, depositing an encapsulant on the semiconductor die and the temporary carrier, forming a first insulating layer on the semiconductor die and the encapsulant, forming a plurality of first vias penetrating the first insulating layer and the semiconductor die while the semiconductor die is mounted on the temporary carrier, forming a plurality of second vias penetrating the first insulating layer and the encapsulant while the semiconductor die is mounted on the temporary carrier, depositing a conductive material into the first vias to form conductive through-silicon vias (TSVs), depositing a conductive material into the second vias to form conductive through-mold vias (TMVs), forming a first interconnect structure on the first insulating layer and electrically connecting to the conductive TSVs and the conductive TMVs, removing the temporary carrier, and forming a second interconnect structure on the encapsulant that is on the opposite side of the semiconductor die and the first interconnect structure and electrically connecting to the conductive TSVs and the conductive TMVs.
Patent document 3 describes a semiconductor device including a first semiconductor chip, the first semiconductor chip having at least one conductive contact on a first side of the first semiconductor chip, a base layer in contact with at least one conductive contact of the first semiconductor chip, the first redistribution layer extending beyond the boundary of the first semiconductor chip, a second semiconductor chip having a first side and a second side and having at least one conductive contact on the first side of the second semiconductor chip, and an adhesive layer disposed between the first side of the first semiconductor chip and the second side of the second semiconductor chip, the second semiconductor chip being disposed directly on the adhesive layer.

JP 2005-183880 A US Patent Application Publication No. 2011/0204505 US Patent Application Publication No. 2014/0015131

In conventional methods for producing cured products using resin compositions containing a polyimide precursor, a polybenzoxazole precursor, or a polyamideimide precursor, there is a demand for improving the aspect ratio of the pattern made of the cured product.

The present invention aims to provide a method for producing a composite pattern that can produce a composite pattern with a high aspect ratio, a resin composition used in the method for producing the composite pattern, a method for producing a laminate that includes the method for producing the composite pattern, and a method for producing a semiconductor device that includes the method for producing the composite pattern or the method for producing the laminate.

Examples of typical embodiments of the present invention are given below.
<1> a first film forming step of applying a first resin composition onto a substrate to form a first photosensitive film;
a first exposure step of selectively exposing the first photosensitive film;
a first development step of developing the first photosensitive film after exposure to form a first pattern;
a second film-forming step of applying a second resin composition onto the first pattern and onto the area where the first pattern has been removed by the first developing step to form a second photosensitive film;
a second exposure step of selectively exposing the second photosensitive film;
a second development step of developing the second photosensitive film after exposure to form a second pattern; and
A modification step of modifying the first pattern and the second pattern at the same time,
The first resin composition contains resin A,
The resin A is at least one selected from the group consisting of a polyimide precursor, a polyimide precursor having a polyimide structure, a polybenzoxazole precursor, a polybenzoxazole precursor having a polybenzoxazole structure, a polyamideimide precursor, and a polyamideimide precursor having a polyamideimide structure.
A method for manufacturing a composite pattern.
<2> The method for producing a composite pattern according to <1>, wherein the resin A has a polymerizable group.
<3> The method for producing a composite pattern according to <1> or <2>, wherein a ratio of a cyclization rate of the resin A in the first pattern after the second development step to a cyclization rate of the resin A in the first pattern after the first development step is 1.1 times or less.
<4> a first film forming step of applying a first resin composition onto a substrate to form a first photosensitive film;
a first exposure step of selectively exposing the first photosensitive film;
a first development step of developing the first photosensitive film after exposure to form a first pattern;
a second film-forming step of applying a second resin composition onto the first pattern and onto the area where the first pattern has been removed by the first developing step to form a second photosensitive film;
a second exposure step of selectively exposing the second photosensitive film;
a second development step of developing the second photosensitive film after exposure to form a second pattern; and
A modification step of modifying the first pattern and the second pattern at the same time,
The second pattern is formed so as to cover at least a part of the first pattern,
a portion of the base material that was in contact with the portion of the first photosensitive film that was removed during the first development step has a region that is in contact with the second pattern and a region that is not in contact with the second pattern;
A method for manufacturing a composite pattern.
<5> The method for producing a composite pattern according to any one of <1> to <4>, wherein the first resin composition contains a polymerizable compound.
<6> The method for producing a composite pattern according to <5>, wherein the first resin composition contains a tri- or higher functional polymerizable compound as the polymerizable compound.
<7> The method for producing a composite pattern according to any one of <1> to <6>, wherein the second resin composition contains a resin B.
<8> The method for producing a composite pattern according to <7>, wherein the resin B is at least one selected from the group consisting of a polyimide precursor, a polyimide precursor having a polyimide structure, a polybenzoxazole precursor, a polybenzoxazole precursor having a polybenzoxazole structure, a polyamideimide precursor, a polyamideimide precursor having a polyamideimide structure, and an epoxy resin.
<9> The method for producing a composite pattern according to any one of <1> to <8>, wherein a remaining film rate of the first pattern to which the second developing step has been applied is 70% or more.
<10> The method for producing a composite pattern according to any one of <1> to <9>, wherein the first resin composition does not contain a colorant.
<11> The method for producing a composite pattern according to any one of <1> to <10>, wherein the modification step is a heating step of heating the first pattern and the second pattern at the same time.
<12> The method for producing a composite pattern according to any one of <7> to <11>, wherein the resin A and the resin B are resins containing repeating units represented by the same structural formula.
<13> The method for producing a composite pattern according to any one of <1> to <12>, wherein a ratio S2/S1 of a dissolution rate S1 of the first photosensitive film in a developer in a first developing step to a dissolution rate S2 of the second photosensitive film in a developer in a second developing step is 1.05 or more.
<14> A first resin composition for use in forming a first photosensitive film in the method for producing a composite pattern according to any one of <1> to <13>.
<15> A second resin composition for use in forming a second photosensitive film in the method for producing a composite pattern according to any one of <1> to <13>.
<16> The method for producing a composite pattern according to any one of <1> to <13> is applied a plurality of times.
A method for manufacturing a laminate.
<17> The method for producing a laminate according to <16>, further comprising a metal layer forming step of forming a metal layer on a layer consisting of the composite pattern, the metal layer forming step being included between steps of applying the production method for the composite pattern a plurality of times.
<18> A method for producing a semiconductor device, comprising the method for producing a composite pattern according to any one of <1> to <13>, or the method for producing a laminate according to <16> or <17>.

The present invention provides a method for producing a composite pattern that can produce a composite pattern with a high aspect ratio, a resin composition used in the method for producing the composite pattern, a method for producing a laminate that includes the method for producing the composite pattern, and a method for producing a semiconductor device that includes the method for producing the composite pattern or the method for producing the laminate.

The main embodiments of the present invention will be described below, however, the present invention is not limited to the embodiments explicitly described.
In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values before and after "to" as the lower limit and upper limit, respectively.
In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, so long as the process can achieve its intended effect.
In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, an "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
In this specification, unless otherwise specified, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams, ion beams, etc. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".
In this specification, in the structural formulae, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent, and in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) method, and are defined as polystyrene equivalent values, unless otherwise stated. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns. Unless otherwise stated, these molecular weights are measured using THF (tetrahydrofuran) as an eluent. However, when THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) light detector with a wavelength of 254 nm.
In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is sufficient that there is another layer above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer. In addition, unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertical upward direction.
In this specification, unless otherwise specified, the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, unless otherwise specified, the temperature is 23° C., the pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
As used herein, combinations of preferred aspects are more preferred aspects.

(Method of manufacturing composite pattern)
In a first embodiment of the method for producing a composite pattern of the present invention, the method for producing a composite pattern includes a first film-forming step of applying a first resin composition onto a substrate to form a first photosensitive film, a first exposure step of selectively exposing the first photosensitive film, a first development step of developing the first photosensitive film after exposure to form a first pattern, a second film-forming step of applying a second resin composition onto the first pattern and onto an area where the first pattern has been removed by the first development step to form a second photosensitive film, and a second exposure step of selectively exposing the second photosensitive film. a developing step of developing the second photosensitive film after exposure to form a second pattern, and a modifying step of modifying the first pattern and the second pattern at the same time, wherein the first resin composition contains resin A which is at least one resin selected from the group consisting of polyimide precursors, polyimide precursors containing a polyimide structure, polybenzoxazole precursors, polybenzoxazole precursors containing a polybenzoxazole structure, polyamideimide precursors, and polyamideimide precursors containing a polyamideimide structure.
In a second embodiment of the method for producing a composite pattern of the present invention, the method for producing a composite pattern includes a first film-forming step of applying a first resin composition onto a substrate to form a first photosensitive film, a first exposure step of selectively exposing the first photosensitive film, a first development step of developing the first photosensitive film after exposure to form a first pattern, a second film-forming step of applying a second resin composition onto the first pattern and onto a region where the first pattern has been removed by the first development step to form a second photosensitive film, and a second development step of forming a second photosensitive film on the second pattern. The method includes a second exposure step of selectively exposing a photosensitive film, a second development step of developing the exposed second photosensitive film to form a second pattern, and a modification step of modifying the first pattern and the second pattern at once, wherein the second pattern is formed so as to cover at least a part of the first pattern, and a portion of the substrate that was in contact with the portion of the first photosensitive film that was removed during the first development step has an area that is in contact with the second pattern and an area that is not in contact with the second pattern.

In the present invention, a composite pattern refers to a pattern including at least a first pattern and a second pattern. The first pattern and the second pattern may be in contact with each other at least in a part, or may not be in contact with each other, but are preferably in contact with each other.
It is also preferable that the top of the first pattern and the bottom of the second pattern are in contact with each other at least in part.
Additionally, the composite pattern may further include a third pattern, a fourth pattern, and so on.

The aspect ratio of a composite pattern is the ratio of the height to the width of the pattern. The height of the pattern is measured as the film thickness of the pattern using an ellipsometer. The width of the pattern is measured as the maximum line width of the pattern for a line pattern, the maximum diameter of the pattern for a pillar pattern, the maximum hole width for a trench pattern, or the maximum hole diameter for a hole pattern by cutting the pattern and observing the cross section with a scanning electron microscope.

The method for producing a composite pattern of the present invention results in a pattern with a high aspect ratio.
The mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.

The method for producing a composite pattern of the present invention is an embodiment in which the film-forming step, the exposure step, and the development step are repeated multiple times, and then the modification step is carried out once.
According to this embodiment, a pattern with a high aspect ratio, particularly a fine trench or hole pattern, can be formed.
In the case of forming a composite pattern by a conventional method in which a film-forming step, an exposure step, a development step, and a modification step are repeated multiple times, it has been difficult to form a pattern with a high aspect ratio due to the influence of shrinkage of a cured product caused by modification, etc. For example, when a pattern with a high aspect ratio is formed by stacking patterns, it may be difficult to form a pattern with a high aspect ratio due to the influence of the number of times of shrinkage caused by modification being different in the pattern.
According to the present invention, it is believed that since the first photosensitive film and the second photosensitive film are modified at the same time, a pattern with a high aspect ratio can be formed.
Furthermore, after forming a first pattern, a second photosensitive film can be formed to cover the first pattern, thereby increasing the line width of the first pattern and forming a second pattern in areas where the first pattern does not exist, thereby forming a denser pattern.

Here, Patent Document 1 does not describe a modification step in which the first photosensitive film and the second photosensitive film are modified at the same time.
The method for producing a composite pattern of the present invention will now be described in detail.
Unless otherwise specified, the first film-forming step, the first exposure step, the first development step, the second film-forming step, the second exposure step, the second development step, the modification step and other steps in the first embodiment and the second embodiment are similar to each other.

<First film formation process>
The method for producing a composite pattern of the present invention includes a first film forming step of applying a first resin composition onto a substrate to form a first photosensitive film.
The first resin composition used in the present invention will be described in detail later.

[Substrate]
The type of substrate can be appropriately determined depending on the application, but includes semiconductor preparation substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates in which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDPs), and are not particularly restricted. In the present invention, semiconductor preparation substrates, Cu substrates, and mold substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.
Furthermore, these substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface.
The substrate may be subjected to a dehydration bake treatment. For example, when forming an adhesive layer of HMDS on the substrate, examples of the embodiment include a mode in which the substrate is heated (dehydration baked) at a temperature of 120° C. or the like while HMDS vapor is brought into contact with the substrate, and a mode in which the substrate is heated (dehydration baked) at a temperature of 120° C. or the like and, after the heating is completed, HMDS vapor is brought into contact with the substrate.
Furthermore, the substrate may be subjected to an oxygen plasma treatment.
The shape of the substrate is not particularly limited, and may be circular or rectangular.
The size of the substrate is, for example, a diameter of 100 to 450 mm, preferably 200 to 450 mm, if it is circular, and, for example, a length of a short side of 100 to 1000 mm, preferably 200 to 700 mm, if it is rectangular.
As the substrate, for example, a plate-shaped substrate, preferably a panel-shaped substrate (substrate) is used.

In addition, when a resin composition is applied to the surface of a resin layer (e.g., a layer made of a cured product) or to the surface of a metal layer to form a film, the resin layer or metal layer becomes the substrate.

Coating is a preferred means for applying the first resin composition onto the substrate.

Specific examples of the means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet methods. From the viewpoint of uniformity of the thickness of the film, more preferred are spin coating, slit coating, spray coating, or inkjet methods, and from the viewpoint of uniformity of the thickness of the film and productivity, spin coating and slit coating are preferred. By adjusting the solid content concentration and coating conditions of the first resin composition according to the method, a film of a desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and if the substrate is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred. In the case of the spin coating method, for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.
Alternatively, a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
Regarding the transfer method, the methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention.
Also, a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing.
In addition, a pre-wetting process may be adopted in which the substrate is coated with various solvents before the first resin composition is applied to the substrate to improve the wettability of the substrate, and then the first resin composition is applied.

<First drying step>
After the first film-forming step (layer-forming step), the first photosensitive film may be subjected to a step (first drying step) of drying the formed film (layer) to remove the solvent.
That is, the method for producing a composite pattern of the present invention may include a first drying step of drying the film formed in the first film forming step.
The first drying step is preferably carried out after the first film-forming step and before the first exposure step.
The drying temperature of the membrane in the first drying step is preferably 50 to 150° C., more preferably 70 to 130° C., and even more preferably 90 to 110° C. Drying may be performed under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

<First Exposure Step>
The first photosensitive film is subjected to a first exposure step of selectively exposing the first photosensitive film to light.
That is, the method for producing a composite pattern of the present invention includes a first exposure step of selectively exposing the first photosensitive film formed in the first film formation step.
Selective exposure means that only a portion of the film is exposed, resulting in exposed and unexposed areas of the film.
The amount of exposure light is not particularly limited as long as it can cure the first resin composition, but is preferably 50 to 10,000 mJ/cm ² , and more preferably 200 to 8,000 mJ/cm ² , calculated as exposure energy at a wavelength of 365 nm.

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

In terms of the light source, the exposure wavelength may be, in particular, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532 nm and third harmonic 355 nm of YAG laser, etc. For the first resin composition, exposure by a high pressure mercury lamp is particularly preferred, and among these, exposure by i-line is preferred. This makes it possible to obtain a particularly high exposure sensitivity.
The exposure method is not particularly limited as long as it is a method in which at least a portion of the film made of the first resin composition is exposed, and examples of the exposure method include exposure using a photomask and exposure by a laser direct imaging method.

<First Post-Exposure Bake Step>
The first photosensitive film may be subjected to a step of heating after exposure (first post-exposure heating step).
That is, the method for producing a composite pattern of the present invention may include a post-first exposure baking step of heating the first photosensitive film exposed in the first exposure step.
The first post-exposure baking step can be carried out after the first exposure step and before the first development step.
The heating temperature in the first post-exposure baking step is preferably from 50°C to 140°C, and more preferably from 60°C to 120°C.
The heating time in the first post-exposure baking step is preferably from 30 seconds to 300 minutes, and more preferably from 1 minute to 10 minutes.
The heating rate in the first post-exposure heating step is preferably from 1 to 12° C./min, more preferably from 2 to 10° C./min, and even more preferably from 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature.
The rate of temperature rise may be appropriately changed during heating.
The heating means in the first post-exposure baking step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.
It is also preferable that the heating be performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

<First Development Step>
The first photosensitive film after exposure is subjected to a first development step in which the first photosensitive film is developed with a developer to form a pattern.
That is, the method for producing a composite pattern of the present invention includes a first development step of developing the first photosensitive film exposed in the first exposure step to form a first pattern. By performing the development, one of the exposed and unexposed parts of the film is removed to form the first pattern.
The development is preferably carried out using a developer.
Here, development in which the non-exposed parts of the film are removed by development is called negative development, and development in which the exposed parts of the film are removed by development is called positive development.

[Developer]
The developer used in the first developing step may be an aqueous alkaline solution or a developer containing an organic solvent.

When the developer is an alkaline aqueous solution, examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferably TMAH. When TMAH is used, the content of the basic compound in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.3 to 3% by mass, based on the total mass of the developer.

When the developer contains an organic solvent, the organic solvent may be, for example, an ester, such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g. methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvic acid Methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like; and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether ... Suitable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; suitable examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; suitable examples of the sulfoxides include dimethyl sulfoxide; suitable examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol; and suitable examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.

When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The content may be 100% by mass.

The developer may further comprise other components.
Examples of other components include known surfactants and known defoamers.

[Method of Supplying Developer]
The method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film is formed in the developer, a paddle development method in which a developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred.
Alternatively, a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times.
As a method of supplying the developer in the first developing step, a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps can be adopted.

The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly specified, but is preferably 10 to 45°C, more preferably 18°C to 30°C.

In the first development step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a method may be adopted in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[Rinse solution]
When the developer is an alkaline aqueous solution, the rinse liquid may be, for example, water. When the developer is an organic solvent-containing developer, the rinse liquid may be, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer).

When the rinse solution contains an organic solvent, examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxypropionate, propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g. methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyrubicin, Examples of suitable ethers include methyl phosphate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like; and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono Suitable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; suitable examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; suitable examples of the sulfoxides include dimethyl sulfoxide; suitable examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol; and suitable examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, with cyclopentanone, γ-butyrolactone, dimethylsulfoxide, PGMEA, and PGME being more preferred, and cyclohexanone and PGMEA being even more preferred.

When the rinse solution contains an organic solvent, the rinse solution preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. In addition, the rinse solution may contain 100% by mass of the organic solvent.

The rinse solution may further contain other ingredients.
Examples of other components include known surfactants and known defoamers.

[Method of Supplying Rinse Liquid]
The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples of the method include a method of immersing the substrate in the rinse liquid, a paddle-type supply on the substrate, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid may be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, while from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.
That is, the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle.
As a method of supplying the rinsing liquid in the rinsing step, a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps can be used.

The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.

<Second Film Forming Step>
The method for producing a composite pattern of the present invention includes a second film formation step of applying a second resin composition onto the first pattern and onto the area from which the first pattern has been removed by the first development step to form a second photosensitive film.
The second resin composition used in the present invention will be described in detail later.

Methods for applying the second resin composition include methods similar to those for applying the first resin composition in the first film formation process described above, and preferred aspects are also similar.

<Second drying step>
After the second film-forming step (layer-forming step), the second photosensitive film may be subjected to a step (second drying step) of drying the formed film (layer) to remove the solvent.
That is, the method for producing a composite pattern of the present invention may include a second drying step of drying the film formed in the second film forming step.
The second drying step is preferably carried out after the second film-forming step and before the second exposure step.
The drying method in the second drying step may be the same as the drying method in the first drying step described above, and the preferred embodiments are also the same.

<Second Exposure Step>
The second photosensitive film is subjected to a second exposure step in which the second photosensitive film is selectively exposed to light.
That is, the method for producing a composite pattern of the present invention includes a second exposure step of selectively exposing the second photosensitive film formed in the second film formation step.
The exposure method in the second exposure step may be the same as the exposure method in the first exposure step described above, and the preferred embodiments are also the same.

<Second Post-Exposure Bake Step>
The second photosensitive film may be subjected to a step of heating after exposure (second post-exposure heating step).
That is, the method for producing a composite pattern of the present invention may include a second post-exposure baking step of heating the second photosensitive film exposed in the second exposure step.
The second post-exposure baking step can be carried out after the second exposure step and before the second development step.
The heating method in the second post-exposure baking step can be the same as the heating method in the first post-exposure baking step described above, and preferred embodiments are also the same.

<Second Development Step>
The second photosensitive film after exposure is subjected to a second development step in which the film is developed with a developer to form a pattern.
That is, the method for producing a composite pattern of the present invention includes a second development step of developing the second photosensitive film exposed in the second exposure step to form a second pattern. By performing the development, one of the exposed and unexposed parts of the film is removed to form the second pattern.
The development is preferably carried out using a developer.
The developing method in the second developing step may be the same as the developing method in the first developing step described above, and the preferred embodiments are also the same.

In a second aspect of the composite pattern of the present invention, the second pattern is formed so as to cover at least a part of the first pattern. In the above aspect, the second pattern may cover at least a part of the first pattern, but it is preferable that the second pattern covers all of the top and side surfaces of the first pattern.
In the second aspect, the portion of the substrate that was in contact with the portion of the first photosensitive film that was removed during the first development step has a region that is in contact with the second pattern and a region that is not in contact with the second pattern, i.e., after the second pattern is formed, at least a portion of the substrate is exposed.
According to such an embodiment, for example, it is possible to form a pattern on the side of the first pattern that is even finer than the first pattern due to the shrink effect of the second photosensitive film, and it is possible to form a fine pattern with a high aspect ratio, for example an aspect ratio of 3:1 or more.
In the first aspect of the composite pattern of the present invention, the second pattern may be formed so as to cover at least a part of the first pattern.
In addition, in the first aspect of the composite pattern of the present invention, the second pattern may be formed in contact with only the upper surface of the first pattern, or the second pattern may be formed in contact with surfaces other than the upper surface of the first pattern.
The position of such a second pattern can be adjusted by the exposure conditions and exposure position in the second exposure step, the development method in the second development step, and the like.

From the viewpoint of forming a composite pattern with a high aspect ratio, the ratio (cyclization rate 2/cyclization rate 1) of the cyclization rate of resin A in the first pattern after the second development step to the cyclization rate of resin A in the first pattern after the first development step (cyclization rate 1) is preferably 1.1 or less, more preferably 1.07 or less, and even more preferably 1.05 times or less.
The lower limit of the cyclization rate is not particularly limited, but is, for example, 1.0 times or more.
Here, the cyclization rate 1 means the cyclization rate of resin A in the first pattern after the first development step and before the second development step is applied. The resin A will be described later.
The cyclization rate of resin A is calculated by the method described in the examples described below.

From the viewpoint of forming a composite pattern with a high aspect ratio, it is preferable that the remaining film ratio of the first pattern is 70% or more after the second pattern is formed (after the second developing step is completed).
The residual film ratio is preferably 70% or more, and more preferably 85% or more. The upper limit of the residual film ratio is not particularly limited, and may be 100%.
The residual film rate is calculated by the method described in the Examples section below.

When producing a composite pattern with a high aspect ratio, from the viewpoint of suppressing the generation of residues, it is preferable that the ratio S2/S1 of the dissolution rate S1 of the first photosensitive film in the developer in the first development step to the dissolution rate S2 of the second photosensitive film in the developer in the second development step is 1.05 or more.
The S2/S1 ratio is preferably 1.07 or more, and more preferably 1.10 or more. The upper limit of the S2/S1 ratio is not particularly limited, but is preferably 2 or less.

<Modification step>
The method for producing a composite pattern of the present invention includes a modification step of modifying the first pattern and the second pattern at the same time.
The denaturing step is preferably a heating step in which the first pattern and the second pattern are heated at the same time.
By the above-mentioned modification step, a composite pattern including the first pattern and the second pattern can be formed.
In the present disclosure, "the first pattern and the second pattern are modified at the same time" means that a step of modifying only the first pattern is not substantially included before the modification step. In other words, a step of modifying only the first pattern is not intentionally included before the modification step. However, this does not apply to reactions caused by unreacted components that may be contained in the first pattern in each step for forming the second pattern after the first pattern is formed.
For example, the modification step may be carried out in the following manner.
- A step of simultaneously heating and denaturing the first pattern and the second pattern - A step of simultaneously heating and denaturing the first pattern and the second pattern in multiple stages - Including a step of simultaneously heating and denaturing the first pattern and the second pattern two or more times - Including a step of simultaneously heating and denaturing the first pattern and the second pattern two or more times As described above, if the step of denaturing the first pattern and the second pattern is simultaneous, that is, the first pattern and the second pattern are denatured in the same process stage and under the same conditions, the same denaturation step may be applied multiple times, or different denaturation steps may be applied in combination.

[Heating process]
The first pattern obtained by the first developing step and the second pattern obtained by the second developing step (each of which is a pattern after rinsing, if rinsing is performed) may be subjected to a heating step in which these patterns are heated at the same time.
That is, the method for producing a composite pattern of the present invention may include a heating step of simultaneously heating the first pattern obtained in the first developing step and the second pattern obtained in the second developing step.
In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide.
Furthermore, a crosslinking reaction of unreacted crosslinkable groups that may be contained in the first resin composition and the second resin composition also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 240°C.

The heating process is preferably a process for promoting a cyclization reaction of the polyimide precursor, etc., within the first pattern and/or the second pattern by the action of a base, etc., generated from a base generator by heating.

The heating step is preferably performed at a temperature rise rate of 1 to 12° C./min from the starting temperature to the maximum heating temperature. The temperature rise rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min. By setting the temperature rise rate at 1° C./min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature rise rate at 12° C./min or less, it is possible to alleviate the residual stress in the composite pattern.
In addition, in the case of an oven capable of rapid heating, the temperature is increased from the starting temperature to the maximum heating temperature at a rate of preferably 1 to 8° C./sec, more preferably 2 to 7° C./sec, and even more preferably 3 to 6° C./sec.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating to the maximum heating temperature. For example, when the first resin composition or the second resin composition of the present invention is applied to a substrate and then dried, it means the temperature of the film (layer) after this drying. For example, it is preferable to raise the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in these resin compositions.

The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming a multi-layer laminate, from the viewpoint of adhesion between layers, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher.
The upper limit of the heating temperature is preferably 350° C. or less, more preferably 250° C. or less, and even more preferably 240° C. or less.

Heating may be performed stepwise. For example, a process may be performed in which the temperature is increased from 25°C to 120°C at 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 180°C at 2°C/min, and held at 180°C for 120 minutes. It is also preferable to perform the process while irradiating ultraviolet rays as described in U.S. Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, a first pretreatment process may be performed in the range of 100 to 150°C, and then a second pretreatment process may be performed in the range of 150 to 200°C.
Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.

The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[Post-development exposure process]
The first pattern obtained by the first developing step and the second pattern obtained by the second developing step (each of the patterns after rinsing, if rinsing is performed) may be subjected to a post-development exposure step in which the pattern after the developing step is exposed to light instead of or in addition to the heating step.
That is, the method for producing a composite pattern of the present invention may include a post-development exposure step of exposing the first pattern obtained by the first development step and the second pattern obtained by the second development step. The method for producing a composite pattern of the present invention may include a heating step and a post-development exposure step as a modification step, or may include only one of the heating step and the post-development exposure step.
In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like proceeds due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group proceeds due to exposure of a photoacid generator to light, can be promoted.
In the post-development exposure step, it is sufficient that at least a portion of the first pattern and the second pattern is exposed, but it is preferable that the entirety of the first pattern and the second pattern is exposed.
The exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , and more preferably 100 to 15,000 mJ/cm ² , calculated as exposure energy at a wavelength to which the photosensitive compound has sensitivity.
The post-development exposure step can be carried out, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.

The method for producing a composite pattern of the present invention may further include a third film formation step of applying a third resin composition onto the second pattern and onto an area from which the second pattern has been removed by the second development step to form a third photosensitive film, a third exposure step of selectively exposing the third photosensitive film, and a third development step of developing the third photosensitive film after exposure to form a third pattern.
According to this embodiment, a three-layer composite pattern is obtained that further includes a third pattern in addition to the first and second patterns.
The third film-forming step, the third exposure step, and the third development step can be carried out in the same manner as the second film-forming step, the second exposure step, and the second development step, respectively, and the preferred embodiments are also the same.
The third film-forming step may be followed by a third drying step, and the third exposure step may be followed by a third post-exposure baking step. The third drying step may be carried out by the same method as the second drying step, and the third post-exposure baking step may be carried out by the same method as the second post-exposure baking step.
Furthermore, by further including a fourth film formation step, a fourth exposure step, a fourth development step, etc. in addition to the third film formation step, the third exposure step, and the third development step, a composite pattern of four or more layers can be obtained.
Furthermore, the third film-forming step, the third exposure step, the third development step, etc. may be carried out after the modification step, but are preferably carried out before the modification step.

<Metal Layer Forming Process>
The composite pattern obtained by the modification step may be subjected to a metal layer forming step of forming a metal layer on the composite pattern.
That is, the method for producing a composite pattern of the present invention preferably includes a metal layer forming step of forming a metal layer on the composite pattern obtained by the modification step.

As the metal layer, any existing metal species can be used without any particular limitation, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods can be considered. More specifically, sputtering, a patterning method that combines photolithography and etching, and a patterning method that combines photolithography and electrolytic plating can be mentioned. A preferred embodiment of plating is electrolytic plating using a copper sulfate or copper cyanide plating solution.

The thickness of the metal layer at its thickest part is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm.

<Applications>
The method for producing a composite pattern of the present invention or the field in which the composite pattern of the present invention can be applied includes insulating films for semiconductor devices, interlayer insulating films for redistribution layers, interlayer insulating films for TSV (through silicon via) or TMV (through mold via), stress buffer films, etc. In addition, examples include etching patterns of sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd. "High-performance and Applied Technology of Polyimide" April 2008, supervised by Masaaki Kakimoto, CMC Technical Library "Basics and Development of Polyimide Materials" published in November 2011, and Japan Polyimide and Aromatic Polymer Research Association/editor "Latest Polyimide Basics and Applications" NTS, August 2010, etc.

The method for producing a composite pattern of the present invention or the composite pattern of the present invention can also be used for producing printing plates such as offset printing plates or screen printing plates, for use in etching molded parts, for producing protective lacquers and dielectric layers in electronics, in particular microelectronics, etc.

<Composite pattern>
The form of the composite pattern obtained by the method for producing a composite pattern of the present invention is not particularly limited, and may be selected according to the application, such as a film, a rod, a sphere, or a pellet. In the present invention, the composite pattern is preferably a film. The shape of the composite pattern can also be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for electrical connection, adjusting impedance, electrostatic capacitance, or internal stress, and providing a heat dissipation function, by pattern processing. The film thickness of the composite pattern is preferably 0.5 μm or more and 150 μm or less.

<Characteristics of composite patterns>
When the first resin composition and/or the second resin composition contains, as resin A and/or resin B, at least one selected from the group consisting of the above-mentioned polyimide precursor, polyimide precursor having a polyimide structure, polybenzoxazole precursor, polybenzoxazole precursor having a polybenzoxazole structure, polyamideimide precursor, and polyamideimide precursor having a polyamideimide structure, the cyclization rate in the composite pattern is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
The breaking elongation of the composite pattern is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the composite pattern is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
When the composite pattern has two or more glass transition temperatures, it is preferred that the lower temperature is within the above range.

(Laminate and method for manufacturing laminate)
The laminate refers to a structure having a plurality of layers each composed of the composite pattern of the present invention.
The laminate of the present invention is a laminate containing two or more layers each composed of a composite pattern, and may be a laminate containing three or more layers.
Of the two or more layers of the composite pattern contained in the laminate, at least one is a layer formed by the composite pattern forming method of the present invention, and from the viewpoint of suppressing shrinkage of the composite pattern or deformation of the composite pattern associated with the shrinkage, it is also preferable that all of the layers of the composite pattern contained in the laminate are layers formed by the composite pattern manufacturing method of the present invention.

That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the composite pattern of the present invention, and more preferably includes repeating the method for manufacturing the composite pattern of the present invention multiple times.

The laminate of the present invention preferably includes two or more layers each formed of a composite pattern, and includes a metal layer between any two adjacent layers each formed of the composite pattern. The metal layer is preferably formed by the metal layer forming step.
That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer consisting of the composite pattern between the steps for producing a composite pattern which are performed multiple times. A preferred embodiment of the metal layer forming step is as described above.
As the above-mentioned laminate, for example, a laminate including at least a layer structure in which three layers, a layer consisting of a first composite pattern, a metal layer, and a layer consisting of a second composite pattern, are laminated in this order, is preferred.
It is preferable that the layer consisting of the first composite pattern and the layer consisting of the second composite pattern are both layers consisting of composite patterns obtained by the method for forming a composite pattern of the present invention. The first resin composition and the second resin composition used to form the layer consisting of the first composite pattern and the first resin composition and the second resin composition used to form the layer consisting of the second composite pattern may be compositions having the same composition or compositions having different compositions.
The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

<Lamination process>
The method for producing the laminate of the present invention preferably includes a lamination step.
The lamination step is a series of steps including carrying out each step in the method for producing a composite pattern of the present invention again on the surface of a pattern (resin layer) or a metal layer. A metal layer forming step may be included after the method for producing a composite pattern of the present invention is carried out multiple times.

When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the composite pattern manufacturing method of the present invention or after the metal layer formation step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

The lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times.
For example, a configuration of 2 to 20 resin layers, such as resin layer (layer consisting of a composite pattern)/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a configuration of 2 to 9 resin layers is even more preferred.
The layers may be the same or different in composition, shape, film thickness, etc.

In a particularly preferred embodiment of the present invention, after providing a metal layer, a composite pattern obtained by the composite pattern manufacturing method of the present invention is further formed so as to cover the metal layer. By alternately performing a lamination step of laminating a layer (resin layer) made of a composite pattern obtained by the composite pattern manufacturing method of the present invention and a metal layer formation step, the layer (resin layer) made of the composite pattern and the metal layer can be alternately laminated.

(Surface activation treatment step)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a part of the layer consisting of the metal layer and the composite pattern.
The surface activation step is usually carried out after the metal layer formation step, but after the above-mentioned modification step, the layer consisting of the composite pattern may be subjected to a surface activation step before the metal layer formation step.
The surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the layer made of the composite pattern, or on at least a part of both the metal layer and the layer made of the composite pattern. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the area of the metal layer on which the layer made of the composite pattern is formed. In this way, by performing the surface activation treatment on the surface of the metal layer, it is possible to improve the adhesion with the layer made of the composite pattern provided on the surface.
In addition, it is preferable to perform the surface activation treatment on a part or the whole of the layer made of the composite pattern. In this way, by performing the surface activation treatment on the surface of the layer made of the composite pattern, it is possible to improve the adhesion with a metal layer or a resin layer provided on the surface that has been surface-activated. In particular, when the layer made of the composite pattern is hardened, such as when performing negative development, it is less likely to be damaged by the surface treatment and adhesion is likely to be improved.
Specifically, the surface activation treatment is selected from plasma treatment with various raw gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment with CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in an aqueous hydrochloric acid solution to remove the oxide film, and then immersion in an organic surface treatment agent containing a compound having at least one amino group and thiol group, and mechanical roughening treatment using a brush, and plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

(Method of manufacturing semiconductor devices)
The present invention also discloses a method for producing a semiconductor device, including the method for producing a composite pattern of the present invention or the method for producing a laminate of the present invention. As a specific example of a semiconductor device using the composite pattern of the present invention for forming an interlayer insulating film for a rewiring layer, the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP2016-027357A can be referred to, and the contents of these are incorporated herein by reference.

(First resin composition)
The first resin composition of the present invention is a resin composition used for forming a first photosensitive film in the method for producing a composite pattern of the present invention.
In a first aspect of the method for producing a composite pattern of the present invention, the first resin composition contains resin A which is at least one resin selected from the group consisting of polyimide precursors, polyimide precursors having a polyimide structure, polybenzoxazole precursors, polybenzoxazole precursors having a polybenzoxazole structure, polyamideimide precursors, and polyamideimide precursors having a polyamideimide structure.
In the first aspect of the method for producing a composite pattern of the present invention, the first resin composition preferably contains the above-mentioned resin A.
Hereinafter, each component contained in the first resin composition of the present invention will be described in detail.

<Resin A>
Resin A is at least one resin selected from the group consisting of polyimide precursors, polyimide precursors containing a polyimide structure, polybenzoxazole precursors, polybenzoxazole precursors containing a polybenzoxazole structure, polyamideimide precursors, and polyamideimide precursors containing a polyamideimide structure.
Resin A is preferably at least one resin selected from the group consisting of polyimide precursors and polyimide precursors containing a polyimide structure.

Resin A preferably contains a polymerizable group, and more preferably contains a radically polymerizable group.
Furthermore, resin A preferably contains a polymerizable group, and more preferably contains a radically polymerizable group.
When the resin A has a radical polymerizable group, the first resin composition of the present invention preferably contains a radical polymerization initiator described later, more preferably contains a radical polymerization initiator described later and also contains a radical crosslinking agent described later. If necessary, the first resin composition of the present invention may further contain a sensitizer described later. For example, a negative photosensitive film is formed from such a first resin composition of the present invention.
Furthermore, the resin A may have a polarity conversion group such as an acid-decomposable group.
When the resin A has an acid-decomposable group, the first resin composition of the present invention preferably contains a photoacid generator described later. From such a first resin composition of the present invention, for example, a chemically amplified positive-type photosensitive film or negative-type photosensitive film is formed.

In addition, it is preferable that the first resin composition does not contain a colorant. When the first resin composition does not contain a colorant, the transparency of the exposure light may be excellent, and the pattern shape may be excellent.

[Polyimide precursor]
The polyimide precursor used in the present invention is not particularly limited in terms of its type, but it preferably contains a repeating unit represented by the following formula (2).
In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

In formula (2), A ¹ and A ² each independently represent an oxygen atom or -NH-, and preferably an oxygen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. As a preferred embodiment of the present invention, a group represented by -Ar- and -Ar-L-Ar- is exemplified, and a group represented by -Ar-L-Ar- is particularly preferred. Here, Ar is each independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a divalent group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, it is preferable that the diamine contains a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and it is more preferable that the diamine contains an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom. Examples of groups containing an aromatic group include the following.

In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO-, or a group selected from combinations thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ₂ -, and further preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -.
In the formula, * represents a bonding site with other structures.

Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl. nyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-amino phenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone , 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane propane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis( 4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3- trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and at least one diamine selected from 4,4'-diaminoquaterphenyl.

Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.

Diamines having two or more alkylene glycol units in the main chain, as described in paragraphs 0032 to 0034 of WO 2017/038598, are also preferably used.

From the viewpoint of flexibility of the resulting organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Here, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a divalent group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

From the viewpoint of i-line transmittance, R ^{111 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-line transmittance and ease of availability, R 111} is more preferably a divalent organic group represented by formula (61).
Equation (51)
In formula (51), R ⁵⁰ to R ⁵⁷ each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ represents a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2).
Examples of the monovalent organic group for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).
In formula (61), R ⁵⁸ and R ⁵⁹ each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2).
Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

In formula (2), R ¹¹⁵ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or (6), each * independently represents a bonding site to another structure.
In formula (5), R ¹¹² is a single bond or a divalent linking group, and is preferably a single bond, or a divalent linking group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, and a combination thereof, more preferably a single bond, or a divalent linking group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO ₂ -, and still more preferably a divalent linking group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, and -SO ₂ -.

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydride. The polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types of tetracarboxylic dianhydride residues as the structure corresponding to R ¹¹⁵ .
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2 ',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyl tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, and alkyl and alkoxy derivatives having 1 to 6 carbon atoms thereof.

Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.

In the formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may have an OH group. More specifically, R ¹¹¹ may be a residue of a bisaminophenol derivative.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. In addition, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both contain a polymerizable group. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. The polymerizable group is a group capable of crosslinking by the action of heat, radicals, etc., and is preferably a radical polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. As the radical polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
In formula (III), * represents a bonding site with another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ —, a cycloalkylene group or a polyalkyleneoxy group.
Suitable examples of R ²⁰¹ include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH ₂ CH(OH)CH ₂ -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH ₂ CH(OH)CH ₂ -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating.The preferred embodiment of the number of repetitions of the ethyleneoxy group in these groups is as described above.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred.
Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

It is also preferable that the polyimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

In order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
Formula (2-A)
In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same definition as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same.
R ¹¹² has the same definition as R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The polyimide precursor has a molecular weight dispersity of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
In this specification, the dispersity of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.
In addition, when the first resin composition contains multiple types of polyimide precursors as resin A, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyimide precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyimide precursors as one resin are each within the above ranges.

[Polyimide precursor containing polyimide structure]
The polyimide precursor containing a polyimide structure is also preferably a resin in which a part of the repeating units represented by formula (2) in the above-mentioned polyimide precursor is ring-closed to form an imide structure.
The imidization rate (also referred to as "ring closure rate") of the polyimide precursor containing a polyimide structure is preferably 25% or less, more preferably 10% or less, and even more preferably 5% or less.
The lower limit of the imidization rate is not particularly limited as long as it is more than 0%.
The imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of the polyimide precursor is measured to determine the peak intensity P1 near 1377 cm ⁻¹ , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C. for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide precursor can be calculated based on the following formula.
Imidization rate (%)=(peak intensity P1/peak intensity P2)×100

[Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly limited with respect to its structure, but preferably contains a repeating unit represented by the following formula (3).
In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ have the same definition as R ¹¹³ in formula (2), and the preferred range is also the same. That is, it is preferable that at least one of them is a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a linear aliphatic group. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. , suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula.

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

As dicarboxylic acids containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting of only a group having an aromatic group and two -COOH groups are more preferred.

In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -, and each * independently represents a bonding site to another structure.

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in formula (2) above, and the preferred range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-4-hydroxyphenyl)hexafluoropropane, and the like. Examples of the bisaminophenols include 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

Among the bisaminophenol derivatives, the following bisaminophenol derivatives having aromatic groups are preferred:

In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- or -NHCO-, and * and # each represent a bonding site with another structure. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. It is also preferable that ^R122 represents a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, it is preferable that, of the total of four * and #, any two are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, and the other two are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and the two * are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and the two # are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, or it is more preferable that the two * are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, and the two # are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and it is even more preferable that the two * are bonding sites with the oxygen atom to which R ¹²² in formula (3) is bonded, and the two # are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded.

The bisaminophenol derivative is also preferably a compound represented by formula (As).

In formula (A-s), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or an organic group selected from the group represented by the following formula (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

(In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (A-s) above.)

In the above formula (A-s), having a substituent at the ortho position of the phenolic hydroxy group, i.e., at R ₃ , is considered to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, and is particularly preferred in that the effect of achieving a high cyclization rate when cured at a low temperature is further enhanced.

In addition, in the above formula (As), it is preferable that R ₂ is an alkyl group and R ₃ is an alkyl group, since this can maintain the effects of high transparency to i-line and a high cyclization rate when cured at a low temperature.

In the above formula (A-s), it is further preferred that R ₁ is an alkylene or a substituted alkylene. Specific examples of the alkylene and substituted alkylene for R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms, of which -CH ₂ -, -CH(CH ₃ )-, and -C(CH ₃ ) ₂ - are more preferred in that they can provide a well-balanced polybenzoxazole precursor that has sufficient solubility in solvents while maintaining the effects of high transparency to i-line and a high cyclization rate when cured at low temperature.

For a method for producing the bisaminophenol derivative represented by the above formula (A-s), reference can be made to, for example, paragraphs [0085] to [0094] and Example 1 (paragraphs [0189] to [0190]) of JP 2013-256506 A, the contents of which are incorporated herein by reference.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, the contents of which are incorporated herein by reference. Needless to say, the invention is not limited to these.

The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating unit of formula (3) above.
The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit, in that the occurrence of warping due to ring closure can be suppressed.

In formula (SL), Z has an a-structure and a b-structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ^2s is a hydrocarbon group having 1 to 10 carbon atoms, and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group, and the remaining are a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. Polymerization of the a-structure and the b-structure may be block polymerization or random polymerization. The mol % of the Z portion is 5 to 95 mol % for the a-structure, 95 to 5 mol % for the b-structure, and a+b is 100 mol %.

In formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration ring closure, and to simultaneously achieve the effect of suppressing warpage and the effect of improving solvent solubility.

When the diamine residue represented by formula (SL) is contained as another type of repeating unit, it is also preferable to further contain a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride as a repeating unit. Examples of such a tetracarboxylic acid residue include the examples of R ¹¹⁵ in formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The polybenzoxazole precursor has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly specified, but is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.
In addition, when the first resin composition contains multiple types of polybenzoxazole precursors as resin A, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polybenzoxazole precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polybenzoxazole precursors as one resin are each within the above ranges.

[Polybenzoxazole precursor containing polybenzoxazole structure]
The polybenzoxazole precursor containing a polybenzoxazole structure preferably has an oxazole ratio (also called "ring closure ratio") of 25% or less, more preferably 10% or less. The lower limit is not particularly limited, and may be more than 0%.
The oxazole ratio is measured, for example, by the following method.
The infrared absorption spectrum of the polybenzoxazole precursor is measured, and the peak intensity Q1 at about 1650 cm ⁻¹ , which is an absorption peak derived from the amide structure of the precursor, is determined. Then, the peak intensity Q1 is normalized by the absorption intensity of the aromatic ring observed at about 1490 cm ⁻¹ . After the polybenzoxazole precursor is heat-treated at 350° C. for 1 hour, the infrared absorption spectrum is measured again, and the peak intensity Q2 at about 1650 cm ⁻¹ is determined and normalized by the absorption intensity of the aromatic ring observed at about 1490 cm ⁻¹ . Using the normalized values of the peak intensities Q1 and Q2 obtained, the oxazole ratio of the polybenzoxazole precursor can be calculated based on the following formula.
Oxazolization rate (%)=(standard value of peak intensity Q1/standard value of peak intensity Q2)×100

[Polyamide-imide precursor]
The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A2 represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In formula (PAI-2), R ¹¹⁷ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.
The above-mentioned linking group is preferably -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.

In addition, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination.
In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound.
Of the three carboxy groups of the tricarboxylic acid compound, two of the carboxy groups may be converted into acid anhydrides.
The optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor includes branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds.
These tricarboxylic acid compounds may be used alone or in combination of two or more.

Specifically, preferred tricarboxylic acid compounds are those containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group combining two or more of these groups via a single bond or a linking group, and more preferred are tricarboxylic acid compounds containing an aromatic group having 6 to 20 carbon atoms, or a group combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, _-CH2- , -C( _CH3 ) _2- , -C( _CF3 )2-, -SO2-, or _a phenylene group.
These compounds may be compounds in which two carboxy groups are anhydridized (e.g., trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

In formula (PAI-2), R ¹¹¹ , A ² and R ¹¹³ have the same meanings as R ¹¹¹ , A ² and R ¹¹³ in formula (2) above, and preferred embodiments are also the same.

The polyamideimide precursor may further comprise other repeat units.
Examples of the other repeating units include the repeating unit represented by the above formula (2) and the repeating unit represented by the following formula (PAI-1).

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group.
In formula (PAI-1), R ¹¹⁶ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.
The above-mentioned linking group is preferably -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.

Also, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having two carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example, i.e., the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound.
These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group.

Specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, and hexadecafluorosuccinic acid. Examples of the fluorosebacic acid include fluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, and benzophenone-4,4'-dicarboxylic acid.
Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups in the specific examples of the dicarboxylic acid compound are halogenated.

In formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in formula (2) above, and preferred embodiments are also the same.

It is also preferable that the polyamideimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more and 20% by mass or less.

In addition, in order to improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine component.

An embodiment of the polyamideimide precursor of the present invention is one in which the total content of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all of the repeating units in the polyamideimide precursor except for the terminals may be any one of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2).
Another embodiment of the polyamideimide precursor of the present invention is one in which the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor except for the terminals may be either the repeating units represented by formula (PAI-2) or the repeating units represented by formula (PAI-1).

The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
The molecular weight dispersity of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly specified, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In addition, when the first resin composition contains multiple types of polyamideimide precursors as resin A, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamideimide precursor are in the above range. In addition, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyamideimide precursors as one resin are each in the above range.

[Polyamideimide precursor containing polyamideimide structure]
The polyamideimide precursor containing a polyamideimide structure is preferably a resin in which a part of the repeating units represented by formula (PAI-2) in the above-mentioned polyamideimide precursor is ring-closed to form an imide structure.
The imidization rate (also referred to as "ring closure rate") in a polyamideimide precursor containing a polyamideimide structure is preferably 25% or less, more preferably 10% or less, and even more preferably 5% or less.
The lower limit of the imidization rate is not particularly limited as long as it is more than 0%.
The imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of the polyamideimide precursor is measured to determine the peak intensity P1 near 1377 cm ⁻¹ , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C. for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyamideimide precursor can be calculated based on the following formula.
Imidization rate (%)=(peak intensity P1/peak intensity P2)×100

[Method for producing polyimide precursor, etc.]
The polyimide precursor or the like can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, and then esterifying the polyamic acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting the diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, etc. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, is more preferable.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.
Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. The organic solvent may be one type or two or more types.
The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.
In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.
The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

-End-capping agent-
In the method for producing a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like in order to further improve storage stability. When capping the carboxylic acid anhydride and acid anhydride derivative remaining at the resin terminal, examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines in terms of reactivity and film stability. Preferred examples of monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of such an acid include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
In addition, when the amino group at the resin terminal is blocked, it is possible to block it with a compound having a functional group capable of reacting with the amino group. Preferred blocking agents for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. Preferred examples of the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

-Solid precipitation-
The production of polyimide precursors and the like may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid as necessary, the obtained polymer component is put into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof to precipitate the polymer component, which is precipitated as a solid and dried to obtain a polyimide precursor and the like. In order to improve the degree of purification, the polyimide precursor and the like may be repeatedly subjected to operations such as redissolving, reprecipitating, and drying. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.

[Content]
The content of resin A in the first resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the first resin composition. The content of the resin in the first resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the first resin composition.
The first resin composition of the present invention may contain only one type of resin A, or may contain two or more types of resin A. When two or more types are contained, the total amount is preferably in the above range.

It is also preferable that the first resin composition of the present invention contains at least two kinds of resins.
Specifically, the first resin composition of the present invention may contain a total of two or more types of resin A and the other resins described below, or may contain two or more types of resin A, but it is preferable that the first resin composition of the present invention contains two or more types of resin A.
When the first resin composition of the present invention contains two or more types of resin A, it is preferable that the resin A contains, for example, two or more types of polyimide precursors having different dianhydride-derived structures (R ¹¹⁵ in the above formula (2)).

<Other resins>
The first resin composition of the present invention may contain the above-mentioned resin A and another resin different from resin A (hereinafter, also simply referred to as "another resin").
Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
For example, by further adding a (meth)acrylic resin, a first resin composition having excellent coatability can be obtained, and a composite pattern having excellent solvent resistance can be obtained.
For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the molar amount of polymerizable groups per 1 g of resin is 1×10 ⁻³ mol/g or more) can be added to the first resin composition, thereby making it possible to improve the coatability of the first resin composition and the solvent resistance of the composite pattern.

When the first resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, relative to the total solid content of the first resin composition.
In addition, the content of the other resin in the first resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, even more preferably 60 mass% or less, and even more preferably 50 mass% or less, relative to the total solid content of the first resin composition.
In addition, as a preferred embodiment of the first resin composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the first resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The first resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.

<Polymerizable Compound>
The first resin composition of the present invention preferably contains a polymerizable compound.
The first resin composition preferably contains a di- or higher functional polymerizable compound, and in one preferred embodiment, it also contains a tri- or higher functional polymerizable compound.
The polymerizable compound may include a radical crosslinking agent or other crosslinking agents.

[Radical Crosslinking Agent]
The first resin composition of the present invention preferably contains a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. The group having an ethylenically unsaturated bond includes a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, and other groups having an ethylenically unsaturated bond.
Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferable.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.
As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
In addition, from the viewpoint of the film strength of the obtained composite pattern, it is also preferable that the first resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxy groups, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. As specific examples, the description in paragraphs [0113] to [0122] of JP2016-027357A can be referred to, and the contents of these are incorporated herein by reference.

In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of such a compound include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, and many other compounds. Examples of suitable polyfunctional acrylates and methacrylates include compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylating the compound, urethane (meth)acrylates as described in JP-B-48-041708, JP-B-50-006034, and JP-A-51-037193, polyester acrylates as described in JP-A-48-064183, JP-B-49-043191, and JP-A-52-030490, and epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, there can be mentioned polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate.

In addition, other preferred radical crosslinking agents that can be used include compounds having a fluorene ring and two or more groups having an ethylenically unsaturated bond, as described in JP-A Nos. 2010-160418, 2010-129825, and Japanese Patent No. 4,364,216, and cardo resins.

Other examples include the specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, and JP-B-01-040336, and the vinylphosphonic acid compounds described in JP-A-02-025493. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in the Journal of the Japan Adhesion Association, Vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of WO 2015/199219 A can also be preferably used, the contents of which are incorporated herein by reference.

In addition, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound, which are described in JP-A-10-062986 as formula (1) and formula (2) along with specific examples thereof, can also be used as radical crosslinking agents.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as radical crosslinking agents, the contents of which are incorporated herein by reference.

As radical crosslinking agents, dipentaerythritol triacrylate (commercially available products include KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd., and A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which the (meth)acryloyl groups of these are bonded via ethylene glycol residues or propylene glycol residues are preferred. Oligomer types of these can also be used.

Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer Corporation; SR-209, 231, and 239, bifunctional methacrylates having four ethyleneoxy chains manufactured by Sartomer Corporation; DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate having three isobutyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.; and urethane acrylate having four ethyleneoxy chains manufactured by Nippon Kayaku Co., Ltd. Examples of such an agent include Ligomer UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmer PME400 (manufactured by NOF Corporation).

As radical crosslinking agents, urethane acrylates as described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton as described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable. Furthermore, as radical crosslinking agents, compounds having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 can also be used.

The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, and particularly preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties during production and excellent developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoints of pattern resolution and film stretchability, it is preferable to use a difunctional methacrylate or acrylate for the first resin composition.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylates having a urethane bond, and bifunctional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as necessary.
For example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a formula weight of about 200 for the polyethylene glycol chain.
In the first resin composition of the present invention, from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the composite pattern, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or higher under normal pressure is also preferred in order to suppress volatilization before exposure.
Other examples of the difunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When a radical crosslinking agent is contained, the content is preferably more than 0% by mass and not more than 60% by mass based on the total solid content of the first resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount is within the above range.

[Other crosslinking agents]
The first resin composition of the present invention preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof under the action of an acid or a base.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As the other crosslinking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred.
Other crosslinking agents include compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is replaced with an acyloxymethyl group, a methylol group, or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and they may be compounds having the same structure as the compounds produced by the above method.In addition, they may be oligomers formed by self-condensation of the methylol groups of these compounds.
As the above amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.
Among these, the first resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents described below.

Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the following urea structure, or on a triazine.
The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, more preferably has 2 or 3 carbon atoms, and even more preferably has 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the above compound is preferably 1,500 or less, and more preferably 180 to 1,200.

R ₁₀₀ represents an alkyl group or an acyl group.
R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group and may be bonded to each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

In the formula, X represents a single bond or a divalent organic group, each of _R104 independently represents an alkyl group or an acyl group, and _R103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to produce an alkali-soluble group (for example, a group that is eliminated by the action of an acid, a group represented by -C( ^R4 ) _2COOR5 (each ^{of R4} independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and ^R5 represents a group that is eliminated by the action of an acid)).
Each R ₁₀₅ independently represents an alkyl group or an alkenyl group; each of a, b, and c independently represents 1 to 3; d represents 0 to 4; e represents 0 to 3; f represents 0 to 3; a+d is 5 or less; b+e is 4 or less; and c+f is 4 or less.
Examples of R ⁵ in a group that decomposes under the action of an acid to generate an alkali-soluble group, a group that is eliminated by the action of an acid, and a group represented by -C(R ⁴ ) ₂ COOR ⁵ include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), etc.
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group, and R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
The alkyl group may be either linear or branched.
The above cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.
The cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms.
The above aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.
Furthermore, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

These groups are preferably tertiary alkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, they are tertiary alkyl ester groups and acetal ester groups.

Specific examples of compounds having an alkoxymethyl group include the following structures: Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compounds has been changed to an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.

The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or may be synthesized by a known method.
From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

Specific examples of urea-based crosslinking agents include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril;
Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea;
ethyleneurea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea;
propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea;
Examples thereof include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used.
Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

Other crosslinking agents may be commercially available, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. , TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, the same applies below) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

It is also preferable that the first resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

-Epoxy compound (compound having an epoxy group)-
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200° C. or less, and does not undergo a dehydration reaction due to the crosslinking, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warping of the first resin composition of the present invention.

It is preferable that the epoxy compound contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group means a group having 2 or more repeating ethylene oxide units, and it is preferable that the number of repeating units is 2 to 15.

Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-830LVP, Epicron (registered trademark) EXA-8183, Epicron (registered trademark) EXA-8169, Epicron (registered trademark) N- 660, Epicron (registered trademark) N-665-EXP-S, Epicron (registered trademark) N-740 (all trade names, manufactured by DIC Corporation), LIKARESIN (registered trademark) BEO-20E, LIKARESIN (registered trademark) BEO-60E, LIKARESIN (registered trademark) HBE-100, LIKARESIN (registered trademark) DME-100, LIKARESIN (registered trademark) L-200 (trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S , EP-3950S (all trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, Epolead (registered trademark) GT401, Epolead (registered trademark) PB4700, Epolead (registered trademark) PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-300 0-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also preferably used.

In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 in order to achieve both heat resistance and improved elongation.

--Oxetane compound (compound having an oxetanyl group)--
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. Specific examples include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more kinds.

-Benzoxazine compound (compound having a benzoxazolyl group)-
Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, they reduce thermal shrinkage and suppress the occurrence of warping.

Preferred examples of benzoxazine compounds include P-d type benzoxazine, F-a type benzoxazine (all trade names, manufactured by Shikoku Kasei Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

The content of the other crosslinking agent is preferably 0.1 to 30 mass% relative to the total solids content of the first resin composition of the present invention, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, it is preferable that the total is within the above range.

[Polymerization initiator]
The first resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat, and particularly preferably contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that generates active radicals by reacting with a photoexcited sensitizer.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L·mol ⁻¹ ·cm ⁻¹ in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.

Any known compound can be used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenones, α-hydroxyketone compounds such as hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For details of these, please refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of WO 2015/199219 A, the contents of which are incorporated herein by reference. Further, the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A and JP 6301489 A, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018/221177 A, photopolymerization initiators described in WO 2018/110179 A, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, and peroxide-based initiators described in JP 2019-167313 A are mentioned, and the contents of these are also incorporated herein.

Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF).

Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF).

As an aminoacetophenone-based initiator, the compounds described in JP 2009-191179 A, which have a maximum absorption wavelength matching a wavelength light source such as 365 nm or 405 nm, can also be used, the contents of which are incorporated herein by reference.

Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins B.V.), IRGACURE-819, and IRGACURE-TPO (product names: all manufactured by BASF) can also be used.

Examples of metallocene compounds include IRGACURE-784, IRGACURE-727, IRGACURE-784EG (all manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

Specific examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232) described compounds, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015/152153, compounds described in WO 2017/051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, compounds described in WO 2013/167515, and the like, the contents of which are incorporated herein.

Preferred oxime compounds include, for example, compounds having the following structure, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the first resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF Corporation), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP-A-2012-014052). In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation) can also be used. Also usable are DFI-091 (manufactured by Daito ChemiX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Also usable are oxime compounds having the following structure:

As the photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compounds described in JP-A-2014-137466 and JP-A-06636081, the contents of which are incorporated herein by reference.

As the photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in International Publication No. 2013/083505, the contents of which are incorporated herein by reference.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-T-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471, the contents of which are incorporated herein by reference.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 A, the contents of which are incorporated herein. In addition, oxime compounds having a nitro group include Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

As the photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in WO 2015/036910.

As a photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include the compounds described in International Publication No. 2019/088055, the contents of which are incorporated herein by reference.

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 in which an electron-withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. The electron-withdrawing group of the aromatic ring group Ar ^OX1 includes an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, and an acyl group is more preferred because it is easy to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and further preferably an alkoxy group, an alkylsulfanyl group, or an amino group.

The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), and more preferably the compound represented by the formula (OX2).
In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group;
R ^X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group;
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.

In the above formula, it is preferable that R ^X12 is an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 and R ^X14 are each a hydrogen atom.

Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

The most preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP 2007-269779 A and oxime compounds having a thioaryl group as disclosed in JP 2009-191061 A, the contents of which are incorporated herein by reference.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, of which at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is even more preferred, and it is even more preferred to use a metallocene compound or an oxime compound.

In addition, examples of the photoradical polymerization initiator that can be used include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenones such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoins, and benzyl derivatives such as benzyl dimethyl ketal. In addition, compounds represented by the following formula (I) can also be used.

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group; R ^I01 is a group represented by formula (II) or is the same group as R ^I00 ; and R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

In addition, the photoradical polymerization initiator may be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015/125469, the contents of which are incorporated herein by reference.

As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, and improving the stability over time of the first resin composition. Specific examples of the bifunctional or trifunctional or higher functional photoradical polymerization initiator include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015/004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017/033680, paragraphs 0039 to 0055; compound (E) and compound (G) described in JP-T-2013-522445; Examples of the photoinitiator include Cmpd1 to 7 described in Japanese Patent Publication No. 34963, the oxime ester photoinitiator described in paragraph 0007 of JP-T-2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of JP-A-2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and the oxime ester photoinitiator described in Japanese Patent No. 6,469,669, the contents of which are incorporated herein by reference.

When a photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% based on the total solid content of the first resin composition of the present invention, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range.
In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[Sensitizer]
The first resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base.
Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like.
Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoethylaminobenzoate Examples of such an alkyl ether compound include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide.
Other sensitizing dyes may also be used.
For details about the sensitizing dye, the description in paragraphs [0161] to [0163] of JP2016-027357A can be referred to, the contents of which are incorporated herein by reference.

When the first resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass% relative to the total solid content of the first resin composition, more preferably 0.1 to 15 mass%, and even more preferably 0.5 to 10 mass%. The sensitizer may be used alone or in combination of two or more types.

[Chain transfer agent]
The first resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of the chain transfer agent include compounds having -S-S-, -SO ₂ -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These donate hydrogen to a low activity radical to generate a radical, or are oxidized and then deprotonated to generate a radical. In particular, thiol compounds can be preferably used.

In addition, the chain transfer agent may be the compound described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.

When the first resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the first resin composition of the present invention. The chain transfer agent may be one type or two or more types. When two or more types of chain transfer agents are used, it is preferable that the total is within the above range.

[Photoacid generator]
The first resin composition of the present invention preferably contains a photoacid generator.
The photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light of 200 nm to 900 nm. The light to be irradiated is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm. The photoacid generator is preferably a photoacid generator that can generate an acid by being exposed to light, either alone or in combination with a sensitizer.
Preferred examples of the acid to be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

Examples of the photoacid generator used in the first resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, and onium salt compounds.
From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of the mechanical properties of the film to be formed, oxime esters are preferred.

Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which the sulfonic acid of quinone diazide is sulfonamide-bonded to a monovalent or polyvalent amino compound, and those in which the sulfonic acid of quinone diazide is ester-bonded and/or sulfonamide-bonded to a polyhydroxy polyamino compound. Although not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds need to be substituted with quinone diazide, it is preferable that on average 40 mol% or more of the total functional groups are substituted with quinone diazide. By incorporating such a quinone diazide compound, a first resin composition that is sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays, can be obtained.

Specific examples of hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisOC P-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML- PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, Tr iML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product names , manufactured by Asahi Yukizai Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), novolak resin and the like can be mentioned, but are not limited to these.

Specific examples of amino compounds include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

Specific examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

Among these, it is preferable that the quinone diazide compound contains an ester of a phenol compound and a 4-naphthoquinone diazide sulfonyl group. This allows for higher sensitivity to i-line exposure and higher resolution.

The content of the quinone diazide compound used in the first resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin. By setting the content of the quinone diazide compound within this range, it is possible to obtain contrast between exposed and unexposed areas, thereby achieving higher sensitivity, which is preferable. Furthermore, a sensitizer or the like may be added as necessary.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably an oxime sulfonate compound represented by the following formula (OS-1), or the below-described formula (OS-103), formula (OS-104), or formula (OS-105).

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of X ³ are present, they may be the same or different. The alkyl group and alkoxy group in X ³ may have a substituent. The alkyl group in X ³ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group in X ^{3 is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in X 3 is} preferably a chlorine atom or a fluorine atom.
In formula (OS-1), m3 represents an integer of 0 to 3, and is preferably 0 or 1. When m3 is 2 or 3, multiple ^X3s may be the same or different.
In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), a compound in which m3 is 3, ^X3 is a methyl group, the substitution position of ^X3 is the ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group is particularly preferred.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs [0064] to [0068] of JP2011-209692A and paragraphs [0158] to [0167] of JP2015-194674A, the contents of which are incorporated herein by reference.

In formulae (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group, or a heteroaryl group; R ^s2 , which may be present in plurality, each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom; R ^s6 , which may be present in plurality, each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group; Xs represents O or S; ns represents 1 or 2; and ms represents an integer of 0 to 6.
In formulae (OS-103) to (OS-105), ^the alkyl group (preferably having 1 to 30 carbon atoms), the aryl group (preferably having 6 to 30 carbon atoms) or the heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R s1 may have a known substituent within the range in which the effects of the present invention can be obtained.

In formulae (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group. Of the R ^s2 , of which two or more may be present in a compound, it is preferable that one or two are an alkyl group, an aryl group or a halogen atom, more preferably that one is an alkyl group, an aryl group or a halogen atom, and particularly preferably that one is an alkyl group and the remaining are a hydrogen atom. The alkyl group or aryl group represented by R ^s2 may have a known substituent within the range in which the effects of the present invention can be obtained.
In formula (OS-103), formula (OS-104), or formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered or 6-membered ring.

In formulae (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2.
In formulae (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent.
In formulae (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Furthermore, the compound represented by formula (OS-103) is particularly preferably a compound represented by formula (OS-106), formula (OS-110) or formula (OS-111) below; the compound represented by formula (OS-104) is particularly preferably a compound represented by formula (OS-107) below; and the compound represented by formula (OS-105) is particularly preferably a compound represented by formula (OS-108) or formula (OS-109) below.

In formulae (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group, or a heteroaryl group; R ^t7 represents a hydrogen atom or a bromine atom; R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group; R ^t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group; and R ^t2 represents a hydrogen atom or a methyl group.
In formulae (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

In formulae (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

In formulae (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ^t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the above oxime sulfonate compound, the stereochemical structure of the oxime (E, Z) may be either one or a mixture.
Specific examples of the oxime sulfonate compounds represented by the above formulae (OS-103) to (OS-105) include the compounds described in paragraphs [0088] to [0095] of JP-A-2011-209692 and paragraphs [0168] to [0194] of JP-A-2015-194674, the contents of which are incorporated herein by reference.

Other preferred embodiments of oxime sulfonate compounds containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. An embodiment in which R ^u9 is a cyano group or an aryl group is more preferable, and an embodiment in which R ^u9 is a cyano group, a phenyl group, or a naphthyl group is even more preferable.
In formula (OS-101) or formula (OS-102), R ^u2a represents an alkyl group or an aryl group.
In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, -CR ^u6 H- or CR ^u6 R ^u7 -, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring with the benzene ring. R ^u1 to R ^u4 are preferably a hydrogen atom, a halogen atom, or an alkyl group, and also preferably an embodiment in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group. Among them, an embodiment in which R ^u1 to R ^u4 are all hydrogen atoms is preferred. Any of the above-mentioned substituents may further have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
In the above oxime sulfonate compound, the stereochemical structures (E, Z, etc.) of the oxime and benzothiazole rings may each be either one or a mixture.
Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs [0102] to [0106] of JP-A-2011-209692 and paragraphs [0195] to [0207] of JP-A-2015-194674, the contents of which are incorporated herein by reference.
Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferable.
Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

Further, compounds represented by the following structural formulas are also preferred examples.

Specific examples of the organic halogenated compounds include those described in Wakabayashi et al., Bull Chem. Soc Japan, vol. 42, pp. 2924 (1969), U.S. Pat. No. 3,905,815, JP-B-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, and M.P. Examples of suitable compounds include those described in Hutt "Journal of Heterocyclic Chemistry" 1 (No. 3), (1970), the contents of which are incorporated herein by reference. In particular, preferred examples include oxazole compounds substituted with a trihalomethyl group: S-triazine compounds.
More preferably, the s-triazine derivative has at least one mono-, di-, or trihalogen-substituted methyl group bonded to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, riazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-i-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-nathoxynaphthyl)-4,6- Examples of the bis(trichloromethyl)-s-triazine include bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

Examples of organic borate compounds are described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916, Japanese Patent No. 2764769, JP-A-2002-116539, and the like, and in Kunz, Martin "Rad Tech'98. Proceedings of April 1998" 19-22, 1998, Chicago", organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561, organic boron iodine complexes described in JP-A-6-175554 and JP-A-6-175553, Specific examples include organoboron transition metal coordination complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, and the like, the contents of which are incorporated herein by reference.

Examples of disulfone compounds include compounds described in JP-A-61-166544 and JP-A-2002-328465, and diazodisulfone compounds.

Examples of the onium salt compounds include diazonium salts described in S. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974) and T. S. Bal et al., Polymer, 21, 423 (1980), ammonium salts described in U.S. Pat. No. 4,069,055 and JP-A-4-365049, phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056, and iodine salts described in European Patent Nos. 104,143, 339,049 and 410,201, JP-A-2-150848 and JP-A-2-296514. sulfonium salts described in European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297,442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827, German Patent Nos. 2,904,626, 3,604,580, and 3,604,581; sulfonium salts described in J. V. Crivello et al., Macromolecules, 10(6), 1307 (1977), J. V. Crivello et al., J. Examples of the onium salt include selenonium salts described in Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), arsonium salts described in C. S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct. (1988), pyridinium salts, and the like, the contents of which are incorporated herein by reference.

Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).
In formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms in the alkyl group or an arylamide group having 6 to 20 carbon atoms in the aryl group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and from the standpoint of stability, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, or a sulfinate ion is preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which the alkyl group each independently has 1 to 12 carbon atoms, an alkylamide group or an arylamide group in which the alkyl group has 1 to 12 carbon atoms, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. ^Z21- represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and is preferably a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion in terms of stability and reactivity. In formula (RI-III), _R31 , _R32 , and _R33 each independently represent an aryl group, an alkyl group, an alkenyl group, or an alkynyl group having 6 to 20 carbon atoms, which may have 1 to 6 substituents, and is preferably an aryl group in terms of reactivity and stability. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, monoalkylamino groups having 1 to 12 carbon atoms, dialkylamino groups in which the carbon number of the alkyl group each independently is 1 to 12 carbon atoms, alkylamide groups or arylamide groups in which the alkyl group has 1 to 12 carbon atoms, carbonyl groups, carboxy groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and from the standpoint of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred.

Specific examples of preferred photoacid generators include the following:

The photoacid generator is preferably used in an amount of 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, even more preferably 0.5 to 10 mass %, still more preferably 0.5 to 3 mass %, and even more preferably 0.5 to 1.2 mass %, based on the total solid content of the first resin composition.
The photoacid generator may be used alone or in combination of two or more kinds. In the case of using a combination of two or more kinds, the total amount thereof is preferably within the above range.
It is also preferable to use a sensitizer in combination to impart photosensitivity to a desired light source.

<Base Generator>
The first resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Examples of the base generator preferred for the first resin composition of the present invention include a thermal base generator and a photobase generator.
In particular, when the first resin composition contains a precursor of a cyclized resin, the first resin composition preferably contains a base generator. By containing the thermal base generator in the first resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the composite pattern can be improved, and the performance as an interlayer insulating film for a rewiring layer included in a semiconductor package can be improved.
The base generator may be an ionic base generator or a non-ionic base generator.
Examples of the base generated from the base generator include secondary amines and tertiary amines.
The base generator according to the present invention is not particularly limited, and a known base generator can be used. Examples of known base generators that can be used include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.
Specific examples of the non-ionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3).

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group not having a tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² are not simultaneously hydrogen atoms. In addition, none of Rb ¹ , Rb ² and Rb ³ has a carboxy group. In this specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when it forms an amide group together with the nitrogen atom.

In formula (B1) and (B2), it is preferable that at least one of Rb ¹ , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and it is preferable that a monocyclic ring or a condensed ring in which two monocyclic rings are condensed. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and it is more preferable that a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and it is more preferable that a cyclohexane ring.

More specifically, Rb ¹ and Rb ² are preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent within the range in which the effects of the present invention are exhibited. Rb ¹ and Rb ² may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle. In particular, ^Rb1 and ^Rb2 are preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

Rb ³ is an alkyl group (having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), an alkenyl group (having 2 to 24 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), an arylalkyl group (having 7 to 23 carbon atoms, preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), an arylalkenyl group (having 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), an alkoxyl group (having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryloxy group (having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an arylalkyloxy group (having 7 to 23 carbon atoms, preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. ^Rb3 may further have a substituent within the range in which the effects of the present invention are exhibited.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2).

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in formula (B1), respectively.
Rb ¹³ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), which may have a substituent within the range in which the effects of the present invention are exhibited. Among these, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferable.

Rb ³⁵ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and an aryl group is preferable.

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are each a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferable.

In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a linking chain connecting adjacent oxygen atoms and carbon atoms, the number of atoms on the linking chain path being 3 or more. Furthermore, ^R and ^R each independently represent a monovalent organic group.

In this specification, the term "linking chain" refers to an atomic chain on a path connecting two atoms or atomic groups to be linked, which links these objects with the shortest distance (the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group, has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "length of the linking chain") is 4.

The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly proceeding with the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO 2020/066416 and the compounds described in paragraphs 0143 to 0177 of WO 2018/038002.

The base generator also preferably contains a compound represented by the following formula (N1).

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic sequence that is the shortest path between the two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), and are preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms). Specific examples include aliphatic hydrocarbon groups (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms) and aromatic hydrocarbon groups (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and are preferably aliphatic hydrocarbon groups. When aliphatic hydrocarbon groups are used as R ^N1 and R ^N2 , the basicity of the generated base is high, and this is preferable. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, the aromatic ring, or the substituent. Particularly, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

Examples of the aliphatic hydrocarbon group constituting R ^N1 and R ^N2 include a linear or branched chain alkyl group, a cyclic alkyl group, a group relating to a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
The cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
The group representing the combination of the linear alkyl group and the cyclic alkyl group preferably has a carbon number of 4 to 24, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the group representing the combination of the linear alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched.
Among these, from the viewpoint of increasing the boiling point of the decomposition product base described below, R ^N1 and R ^N2 are preferably alkyl groups having 5 to 12 carbon atoms. However, in a formulation in which importance is placed on adhesion when laminating with a metal (e.g., copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

R ^N1 and R ^N2 may be linked together to form a cyclic structure. When forming a cyclic structure, an oxygen atom or the like may be included in the chain. In addition, the cyclic structure formed by R ^N1 and R ^N2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. The cyclic structure formed is preferably a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1), for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc., and preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring.

R ^C1 represents a hydrogen atom or a protecting group, and is preferably a hydrogen atom.

As the protecting group, a protecting group that is decomposed by the action of an acid or a base is preferred, and a protecting group that is decomposed by an acid is preferred.

Specific examples of protective groups include linear or cyclic alkyl groups, and linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Specific examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specific examples include methyloxymethyl (MOM) and ethyloxyethyl (EE) groups. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

The divalent linking group constituting L is not particularly specified, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have an atom other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. It is more preferable that these groups do not have an oxygen atom.
The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group relating to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

Specific examples of the linking group L include linear or branched chain alkylene groups, cyclic alkylene groups, groups relating to a combination of a chain alkylene group and a cyclic alkylene group, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups.
The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms.
The group relating to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 3. The linear or branched chain alkenylene group preferably has 1 to 10 C═C bonds, more preferably 1 to 6, and still more preferably 1 to 3.
The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, and more preferably has 1 to 4 C═C bonds, and even more preferably has 1 or 2 C═C bonds.
The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cisvinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

Examples of base generators include the following, but the present invention should not be construed as being limited thereto.

The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018/038002.

Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these.

Specific examples of iminium salts include the following compounds, but the present invention is not limited to these.

When the first resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the first resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

<Solvent>
The first resin composition of the present invention preferably contains a solvent.
The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters ... Preferred examples of the cypropionic acid alkyl esters include methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

A suitable example of a sulfoxide is dimethyl sulfoxide.

Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

It is also preferable to mix two or more types of solvents from the viewpoint of improving the properties of the coating surface.

In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more of them, is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

From the viewpoint of coatability, the content of the solvent is preferably an amount that results in a total solids concentration of the first resin composition of the present invention of 5 to 80% by mass, more preferably an amount that results in a total solids concentration of 5 to 75% by mass, even more preferably an amount that results in a total solids concentration of 10 to 70% by mass, and even more preferably an amount that results in a total solids concentration of 20 to 70% by mass. The content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method.

The first resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more types of solvents are contained, it is preferable that the total amount of the solvents is within the above range.

<Metal adhesion improver>
The first resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, an amino compound, and the like.

[Silane coupling agent]
Examples of silane coupling agents include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062-0073 of JP 2014-191002 A, compounds described in paragraphs 0063-0071 of WO 2011/080992 A, compounds described in paragraphs 0060-0061 of JP 2014-191252 A, compounds described in paragraphs 0045-0052 of JP 2014-041264 A, compounds described in paragraphs 0055 of WO 2014/097594 A, and compounds described in paragraphs 0067-0078 of JP 2018-173573 A, the contents of which are incorporated herein. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compound as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples of such compounds include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These compounds may be used alone or in combination of two or more.

[Aluminum-based adhesion promoter]
Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

In addition, other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of resin A. By making the content equal to or above the lower limit, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or below the upper limit, the heat resistance and mechanical properties of the pattern will be good. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.

<Migration inhibitor>
The first resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.

The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

Alternatively, an ion trapping agent can be used to capture anions such as halogen ions.

Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116 and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219 A, the contents of which are incorporated herein by reference.

Specific examples of migration inhibitors include the following compounds:

When the first resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, relative to the total solids content of the first resin composition of the present invention.

The migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, it is preferable that the total amount of the migration inhibitors is within the above range.

<Polymerization inhibitor>
The first resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.

Specific examples of polymerization inhibitor compounds include p-hydroquinone, o-hydroquinone, methoxyhydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso Phenylhydroxyamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl) N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine Methylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, TAOBN (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dixoid), etc. can be suitably used. In addition, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used, the contents of which are incorporated herein by reference.

When the first resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass%, more preferably 0.02 to 15 mass%, and even more preferably 0.05 to 10 mass%, relative to the total solids content of the first resin composition of the present invention.

The polymerization inhibitor may be one type or two or more types. When two or more types of polymerization inhibitors are used, it is preferable that the total amount is within the above range.

<Acid Scavenger>
The first resin composition of the present invention preferably contains an acid scavenger in order to reduce the performance change over time from exposure to heating. Here, the acid scavenger refers to a compound that can capture generated acid by being present in the system, and is preferably a compound with low acidity and high pKa. As the acid scavenger, a compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. are preferable, and a primary amine, a secondary amine, a tertiary amine, and an ammonium salt are preferable, and a secondary amine, a tertiary amine, and an ammonium salt are more preferable.
Preferred examples of the acid scavenger include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, alkylamine derivatives having a hydroxyl group and/or an ether bond, aniline derivatives having a hydroxyl group and/or an ether bond, etc. When the acid scavenger has an onium structure, it is preferred that the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator.

Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undeca-7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylsulfonium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylamine, ethylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, and the like.

These acid scavengers may be used alone or in combination of two or more.
The composition according to the present invention may or may not contain an acid scavenger. When the composition according to the present invention contains an acid scavenger, the content of the acid scavenger is usually 0.001 to 10 mass %, and preferably 0.01 to 5 mass %, based on the total solid content of the composition.

The ratio of the acid generator to the acid scavenger is preferably acid generator/acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the relief pattern over time until heat treatment after exposure, the molar ratio is preferably 300 or less. The acid generator/acid scavenger (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

<Other additives>
The first resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained. By appropriately incorporating these components, it is possible to adjust the properties of the film, etc. These components can be referred to, for example, in paragraphs 0183 and onward of JP-A-2012-003225 (corresponding to paragraph 0237 of US Patent Application Publication No. 2013/0034812), and in paragraphs 0101 to 0104, 0107 to 0109, etc. of JP-A-2008-250074, the contents of which are incorporated herein. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the first resin composition of the present invention.

[Surfactant]
As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By including a surfactant in the first resin composition of the present invention, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and liquid saving can be further improved. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and improving the coatability of the surface to be coated. This makes it possible to more suitably form a film of uniform thickness with little thickness unevenness.

Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, and Megafac RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171, Novec FC4430, and FC4432 (all manufactured by 3M Corporation). Examples of the fluorine-based surfactant include those described in paragraphs 0015 to 0158 of JP2015-117327A and those described in paragraphs 0117 to 0132 of JP2011-132503A, and the like. Examples of the fluorine-based surfactant include those described in paragraphs 0015 to 0158 of JP2015-117327A and those described in paragraphs 0117 to 0132 of JP2011-132503A, and the contents of which are incorporated herein by reference. A block polymer can also be used as the fluorine-based surfactant. Specific examples include compounds described in JP-A-2011-89090, the contents of which are incorporated herein by reference.
As the fluorosurfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used. The following compounds are also exemplified as the fluorosurfactant for use in the present invention.

The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, and more preferably from 5,000 to 30,000.
As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein by reference. Commercially available products include, for example, Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorine surfactants with a fluorine content within this range are effective in terms of uniformity of the coating film thickness and liquid saving, and also have good solubility in the composition.

Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie Co., Ltd.), etc.

Examples of hydrocarbon surfactants include Paionin A-76, Newcalgen FS-3PG, Paionin B-709, Paionin B-811-N, Paionin D-1004, Paionin D-3104, Paionin D-3605, Paionin D-6112, Paionin D-2104-D, Paionin D-212, Paionin D-931, Paionin D-941, Paionin D-951, Paionin E-5310, Paionin P-1050-B, Paionin P-1028-P, Paionin P-4050-T, etc. (all manufactured by Takemoto Oil Co., Ltd.).

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil Co., Ltd.), Olfine E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.), etc.

The surfactant may be used alone or in combination of two or more kinds.
The content of the surfactant is preferably from 0.001 to 2.0% by mass, and more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition.

[Higher fatty acid derivative]
In order to prevent polymerization inhibition caused by oxygen, the first resin composition of the present invention contains a higher fatty acid derivative such as behenic acid or behenic acid amide, and the composition is dried after application. The first resin composition may be unevenly distributed on the surface of the first resin composition.

In addition, the higher fatty acid derivative may be the compound described in paragraph 0155 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.

When the first resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the first resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total is preferably within the above range.

[Thermal Polymerization Initiator]
The first resin composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. The addition of the thermal radical polymerization initiator can also advance the polymerization reaction of the resin and the polymerizable compound, thereby further improving the solvent resistance. In addition, the above-mentioned photopolymerization initiator may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated herein by reference.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% relative to the total solids content of the first resin composition of the present invention, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be included, or two or more types may be included. When two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

[Ultraviolet absorber]
The composition of the present invention may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbing agents.
Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Further, examples of triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

In the present invention, the above-mentioned various ultraviolet absorbents may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber. When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.001 mass % to 1 mass %, and more preferably from 0.01 mass % to 0.1 mass %, relative to the total solid content mass of the composition of the present invention.

[Organotitanium Compounds]
The first resin composition of the present embodiment may contain an organotitanium compound. By containing the organotitanium compound in the first resin composition, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organotitanium compound are shown below in I) to VII):
I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because the first resin composition has good storage stability and a good curing pattern can be obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate, titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like.
III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.
VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.
VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of resin A. When the blending amount is 0.05 parts by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while when the blending amount is 10 parts by mass or less, the storage stability of the composition is superior.

[Antioxidants]
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials. Examples of the antioxidant include phenolic compounds, phosphite compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, a hindered phenolic compound can be mentioned. A compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group is preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. In addition, a phosphorus-based antioxidant can also be suitably used as the antioxidant. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Examples of commercially available antioxidants include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA CORPORATION). In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as the antioxidant, the contents of which are incorporated herein by reference. In addition, the composition of the present invention may contain a latent antioxidant, if necessary. Examples of latent antioxidants include compounds in which the site functioning as an antioxidant is protected with a protecting group, and the protecting group is removed by heating at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst, and the compound functions as an antioxidant. Examples of latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219 A, the contents of which are incorporated herein by reference. Commercially available latent antioxidants include ADEKA ARCLES GPA-5001 (manufactured by ADEKA Corporation).
Preferred examples of the antioxidant include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the compound represented by formula (3).

In general formula (3), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom, and k represents an integer of 1 to 4.

The compound represented by formula (3) suppresses the oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin. In addition, the compound has a rust-preventing effect on metal materials, thereby suppressing metal oxidation.

Since it can act simultaneously on resins and metal materials, k is preferably an integer between 2 and 4. Examples of R7 include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkyl silyl groups, alkoxy silyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, it is preferable to have an alkyl ether group or -NH- from the viewpoints of solubility in the developer and metal adhesion, and -NH- is more preferable from the viewpoints of interaction with the resin and metal adhesion due to metal complex formation.

Examples of compounds represented by general formula (3) include, but are not limited to, the following structures:

The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By adding an amount of 0.1 part by mass or more, it is easier to obtain the effect of improving elongation properties and adhesion to metal materials even in a high-temperature and high-humidity environment, and by adding an amount of 10 parts by mass or less, the sensitivity of the first resin composition is improved, for example, by interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[Anti-aggregation agent]
The first resin composition of the present embodiment may contain an anti-aggregation agent as necessary. Examples of the anti-aggregation agent include sodium polyacrylate.

In the present invention, the anti-aggregating agent may be used alone or in combination of two or more kinds.
The composition of the present invention may or may not contain an anti-aggregating agent. When the composition of the present invention contains an anti-aggregating agent, the content of the anti-aggregating agent is preferably from 0.01% by mass to 10% by mass, and more preferably from 0.02% by mass to 5% by mass, relative to the total solid content mass of the composition of the present invention.

[Phenol compounds]
The first resin composition of the present embodiment may contain a phenolic compound as necessary. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

In the present invention, the phenolic compounds may be used alone or in combination of two or more.
The composition of the present invention may or may not contain a phenolic compound. When the composition of the present invention contains a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the composition of the present invention.

[Other polymer compounds]
Examples of the other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof, etc. The other polymer compounds may be modified by introducing a crosslinking group such as a methylol group, an alkoxymethyl group, or an epoxy group.

In the present invention, the other polymer compounds may be used alone or in combination of two or more.
The composition of the present invention may or may not contain other polymer compounds. When the composition of the present invention contains other polymer compounds, the content of the other polymer compounds is preferably 0.01 mass % or more and 30 mass % or less, and more preferably 0.02 mass % or more and 20 mass % or less, relative to the total solid content mass of the composition of the present invention.

<Characteristics of the first resin composition>
The viscosity of the first resin composition of the present invention can be adjusted by the solid content concentration of the first resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000 mm ² /s to 12,000 mm ² /s, more preferably 2,000 mm ² /s to 10,000 mm ² /s, and even more preferably 2,500 mm ² /s to 8,000 mm ² /s. If it is within the above range, it is easy to obtain a coating film with high uniformity. If it is 1,000 mm ² /s or more, it is difficult to apply it with a film thickness required for, for example, an interlayer insulating film for a rewiring layer, and if it is 12,000 mm ² /s or less, a coating film with excellent coating surface condition can be obtained.

<Restrictions on substances contained in the first resin composition>
The water content of the first resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass.
If the content is less than 2.0%, the storage stability of the first resin composition is improved.
Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.

From the viewpoint of insulation, the metal content of the first resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, it is preferable that the total of these metals is within the above range.

In addition, examples of methods for reducing metal impurities unintentionally contained in the first resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the first resin composition of the present invention, filtering the raw materials constituting the first resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

Considering the use of the first resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, those present in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

A conventionally known container can be used as the container for the first resin composition of the present invention. In addition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure made of six types of resin, in order to suppress the inclusion of impurities in the raw materials or the first resin composition of the present invention. Examples of such containers include the containers described in JP 2015-123351 A.

<Preparation of first resin composition>
The first resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and the components can be prepared by a conventionally known method.
The mixing can be performed by using a stirring blade, a ball mill, or by rotating the tank itself.
The temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.

In addition, it is preferable to perform filtration using a filter for the purpose of removing foreign matter such as dust and fine particles in the first resin composition of the present invention. The filter pore size may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferable that it is HDPE (high density polyethylene). The filter may be used after being washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. As an example of a connection mode, for example, an HDPE filter with a pore size of 1 μm as the first stage and an HDPE filter with a pore size of 0.2 μm as the second stage may be connected in series. In addition, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be performed. Filtration may also be performed under pressure. When filtration is performed under pressure, the pressure to be applied may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.
In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used.
Furthermore, after filtration using a filter, the first resin composition filled in the bottle may be subjected to a degassing step by placing it under reduced pressure.

(Second Resin Composition)
The second resin composition of the present invention is a resin composition used for forming a second photosensitive film in the method for producing a composite pattern of the present invention.

The second resin composition preferably contains a resin B, and more preferably contains as resin B at least one resin selected from the group consisting of a polyimide precursor, a polyimide precursor containing a polyimide structure, a polybenzoxazole precursor, a polybenzoxazole precursor containing a polybenzoxazole structure, a polyamideimide precursor, a polyamideimide precursor containing a polyamideimide structure, and an epoxy resin.
The polyimide precursor, polyimide precursor having a polyimide structure, polybenzoxazole precursor, polybenzoxazole precursor having a polybenzoxazole structure, polyamideimide precursor, and polyamideimide precursor having a polyamideimide structure in Resin B are similar to the polyimide precursor, polyimide precursor having a polyimide structure, polybenzoxazole precursor, polybenzoxazole precursor having a polybenzoxazole structure, polyamideimide precursor, and polyamideimide precursor having a polyamideimide structure in Resin A described above, respectively, and preferred aspects are also similar.

The epoxy resin in Resin B is not particularly limited, but examples thereof include novolac type epoxy resins, bisphenol type epoxy resins, glycidylamine type epoxy resins, glycidyl ether type epoxy resins, triphenolmethane type epoxy resins, triphenolpropane type epoxy resins, alkyl-modified triphenolmethane type epoxy resins, triazine nucleus-containing epoxy resins, dicyclopentadiene-modified phenol type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having at least one of a phenylene skeleton and a biphenylene skeleton, and naphthol aralkyl type epoxy resins having at least one of a phenylene skeleton and a biphenylene skeleton, and aliphatic epoxy resins.
In addition, when the second resin composition contains an epoxy resin, the epoxy compound described above as the polymerizable compound may be used.

In addition, the details of each component contained in the second resin composition of the present invention, and the physical properties and other characteristics of the second resin composition are the same as those of the first resin composition, and the preferred aspects are also the same.

In the method for producing a composite pattern of the present invention, it is also preferable that the first resin composition and the second resin composition are resin compositions containing a resin containing a repeating unit represented by the same structural formula. That is, it is preferable that the resin A and the resin B are resins containing a repeating unit represented by the same structural formula, and may contain two or more types of repeating units represented by the same structural formula. When the resin A and the resin B are resins containing a repeating unit represented by the same structural formula, the preferred content of the repeating unit represented by the same structural formula is, for example, 30 mol% or more of the total repeating units, and preferably 50 mol% or more. In addition, when two or more types of repeating units represented by the same structural formula are contained, the total content may be within the above range. The upper limit is not particularly limited, and is, for example, 100 mol% or less.
According to the above-mentioned embodiment, it is considered that the effect of shrinkage due to curing is reduced, and it is easy to form a composite pattern with a higher aspect ratio. In addition, a composite pattern having excellent adhesion between the first pattern and the second pattern may be obtained.

The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are by weight unless otherwise specified.

Synthesis Example 1: Synthesis of Polymer P-1
7.76 g (25 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) and 6.23 g (25 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride were placed in a reaction vessel, and 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone were added. 7.91 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and was allowed to stand for a further 16 hours.
Next, a solution of 20.6 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) in 30 ml of γ-butyrolactone was added to the reaction mixture under ice cooling over a period of 40 minutes with stirring, followed by the addition of a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone over a period of 60 minutes with stirring.
After stirring at room temperature for an additional 2 hours, 3 ml of ethyl alcohol was added and stirred for 1 hour, followed by adding 100 ml of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The obtained reaction solution was added to 3 liters of ethyl alcohol to generate a precipitate containing a crude polymer. The generated precipitate containing a crude polymer was filtered and dissolved in 200 ml of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 3 liters of water to obtain a precipitate. The obtained precipitate was filtered and then vacuum dried to obtain a powdered polymer P-1.
The weight average molecular weight (Mw) of this polymer was measured and found to be 23,000.
Polymer P-1 is a resin having the following structure: The subscripts in parentheses indicate the molar ratio of each repeating unit.

Synthesis Example 2: Synthesis of Polymer P-2
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with _SOCl2 , and converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 5, to obtain polymer P-2 in the same manner as in Synthesis Example 5. The weight average molecular weight of polymer P-2 was 29,000.
Polymer P-2 is a resin having the following structure:

Synthesis Example 3: Synthesis of Polymer P-3
15.5 g (50 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a reaction vessel, and 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone were added. 7.91 g of pyridine was added with stirring at room temperature to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and was left to stand for a further 16 hours.
Next, a solution of 20.6 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) in 30 ml of γ-butyrolactone was added to the reaction mixture under ice cooling over a period of 40 minutes with stirring, followed by the addition of a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone over a period of 60 minutes with stirring.
After stirring at room temperature for an additional 2 hours, 3 ml of ethyl alcohol was added and stirred for 1 hour. Then, 100 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The obtained reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate containing a crude polymer. The produced precipitate containing a crude polymer was filtered and dissolved in 200 ml of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 3 liters of water to obtain a precipitate. The obtained precipitate was filtered and then vacuum dried to obtain a powdered polymer P-3.
The weight average molecular weight (Mw) of this polymer P-3 was measured and found to be 27,000.
Polymer P-3 is a resin having the following structure:

Synthesis Example 4: Synthesis of Polymer P-4
14.7 g (50 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was placed in a reaction vessel, and 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone were added. 7.91 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and was left to stand for another 16 hours.
Next, under ice cooling, a solution of 20.6 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 30 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Then, a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) added to 350 ml of γ-butyrolactone was added over 60 minutes while stirring. Thereafter, purification and drying were carried out in the same manner as in Synthesis Example 1 to obtain a polymer P-4. The weight average molecular weight (Mw) of this polymer was measured and found to be 28,000.
Polymer P-4 is a resin having the following structure:

Synthesis Example 5: Synthesis of Polymer P-5
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60°C for 18 hours to produce a reaction mixture containing the diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -5°C, and 16.12 g (135.5 mmol) of _SOCl2 was added over 2 hours while maintaining the temperature at -5±2°C. Next, a solution of 11.32 g (60.0 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was dropped into the reaction mixture over 2 hours while adjusting the temperature to the range of -5 to 0°C. The reaction mixture was reacted at 0°C for 1 hour, and then 70 g of ethanol was added and stirred at room temperature for 1 hour. The reaction mixture was then added to 5 liters of water to precipitate a polyimide precursor, and centrifuged at a speed of 5,000 rpm for 15 minutes. The precipitate was collected by filtration, added to 4 liters of water and stirred again for 30 minutes, and the precipitate was collected by filtration again. The obtained precipitate was then dried under reduced pressure at 45°C for 2 days to obtain polymer P-5. The weight average molecular weight of polymer P-5 was 31,000.
Polymer P-5 is a resin having the following structure:

Synthesis Example 6: Synthesis of Polymer P-6
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The diester obtained was then chlorinated with _SOCl2 , and 4,4'-diaminodiphenyl ether was dissolved in N-methylpyrrolidone in an amount reduced by 2% compared to that of Synthesis Example 5 in the same manner as in Synthesis Example 5, and reacted in the same manner to convert it into a polyimide precursor, and polymer P-6 was obtained in the same manner as in Synthesis Example 5. The weight average molecular weight of polymer P-6 was 18,000.

Synthesis Example 7: Synthesis of Polymer P-7
13.9 g (38 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to a reaction vessel containing 60 g of N-methylpyrrolidone, and dissolved by stirring. Next, 10.7 g (40 mmol) of dodecanedioic acid dichloride was added dropwise over 10 minutes at a temperature range of 0 to 5°C, and then the mixture was stirred for 60 minutes. Next, the reaction solution was poured into 3 liters of water to obtain a precipitate. The precipitate was washed with pure water and then dried to obtain polymer P-7 (polybenzoxazole precursor). The weight average molecular weight of polymer P-7 was 32,000.

<Synthesis Example 8: Synthesis of Polymer P-8>
Under a dry nitrogen stream, 100 g of N-methylpyrrolidone was charged, 32.96 g (90 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g (20 mmol) of m-aminophenol were added, and the mixture was stirred and dissolved at room temperature. Then, 20.04 g (75 mmol) of dodecanedioic acid dichloride was added dropwise over 10 minutes while maintaining the temperature of the reaction solution at -10 to 0°C, and 7.38 g (25 mmol) of 4,4'-diphenyletherdicarboxylic acid chloride was added, and stirring was continued for 3 hours at room temperature. The reaction solution was poured into 3 liters of water, and the precipitate was collected and washed three times with pure water, and then dried for 3 days in a 50°C ventilated dryer to obtain a powder of polybenzoxazole precursor (polymer P-8). The weight average molecular weight of polymer P-8 was 31,000.

Synthesis Example 9: Synthesis of Polymer P-9
Under a dry nitrogen stream, 88.64 g (180 mmol) of dicarboxylate consisting of 4,4'-dicarboxydiphenyl ether and 1-hydroxybenzotriazole, 65.93 g (180 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 12.00 g (20 mmol) of ED-600 (trade name, manufactured by HUNTSMAN Co., Ltd.), and 800 g of NMP were reacted at 25 ° C. for 30 minutes, then heated in an oil bath and reacted at 80 ° C. for 8 hours. Next, 12.31 g (75 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added as a terminal blocking agent, and the reaction was terminated by stirring at 80 ° C. for another 3 hours. After the reaction was completed, the solution was cooled to room temperature, and the reaction mixture was filtered, and the reaction mixture was poured into 2 L of a mixture of water/isopropanol = 3/1 (volume ratio) to obtain a precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 20 hours to obtain Polymer P-9 (polybenzoxazole precursor). The weight average molecular weight of Polymer P-9 was 28,000.

<Examples and Comparative Examples>
The components shown in the table below were mixed to obtain each composition.
Specifically, the contents of the components shown in the table were the amounts shown in the "parts by mass" column of the table.
The obtained composition was pressure filtered through a polytetrafluoroethylene filter having a filter pore size of 0.2 μm.
In the table, "-" indicates that the composition does not contain the corresponding component.

Details of each ingredient listed in the table are as follows:

〔resin〕
P-1 to P-9: P-1 to P-9 synthesized above
P-10: Bisphenol A type epoxy resin (LX-01, manufactured by Daiso Co., Ltd.)
P-11: Alicyclic epoxy resin (manufactured by Daicel Chemical Industries, Ltd., CEL2021)
P-12: Multifunctional epoxy resin (VG-3101L, manufactured by Printec Co., Ltd.)

[Polymerizable Compound]
B-1: Polyethylene glycol methacrylate G4, manufactured by Shin-Nakamura Chemical Co., Ltd.
・B-2: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMMT
B-3: Nikalac MX-270 (manufactured by Sanwa Chemical Co., Ltd.)
B-4: TML-BPA (manufactured by Honshu Chemical Industry Co., Ltd.)
B-5: Celloxide 2021P (manufactured by Daicel Corporation)
B-6: Tetraethylene glycol dimethacrylate B-7: Compound having the following structure B-8: Trimethylolpropane triacrylate (CAS. 15625-89-5)
B-9: Dipentaerythritol hexaacrylate B-10: PR-53365 (manufactured by Sumitomo Bakelite)

[Polymerization initiator]
C-1: Irgacure OXE-01 (manufactured by BASF)
C-2: Irgacure OXE-02 (manufactured by BASF)
C-3: Irgacure 784 (manufactured by BASF)
・C-4: CPI-210S (manufactured by San-Apro Co., Ltd.)
C-5: Lambson G-1820
C-6: A compound obtained by converting the hydroxy group of TrisP-PA (α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene) into diazonaphthoquinone using 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride; C-7: 1-phenyl-2-[(benzoyloxy)imino]-1-propanone; C-8: Irgacure 290 (manufactured by BASF)

[Metal adhesion improver]
D-1: KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.)
D-2: γ-ureidopropyltriethylsilane D-3: N-[3-(triethoxysilyl)propyl]maleamic acid D-4: N-(3-triethoxysilyl)propyl)-phthalamic acid

[Migration Inhibitor]
E-1: 5-aminotetrazole

[Polymerization inhibitor]
F-1: 2MeHQ (methoxyhydroquinone)
F-2: TAOBN (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dixoid)

[Surfactant]
G-1: Megafac F444 (DIC Corporation)

[Base Generator]
H-1: 1-[4-(2-hydroxyethyl)-1-piperidinyl]-3-(2-hydroxyphenyl)-1-propanone

[Additives]
I-1: Compound having the following structure I-2: N-phenyldiethanolamine I-3: Compound having the following structure

〔solvent〕
J-1: GBL (γ-butyrolactone)
J-2: DMSO (dimethyl sulfoxide)
J-3: EL (ethyl lactate)
J-4: NMP (N-methyl-2-pyrrolidone)

(evaluation)
<Preparation of Composite Pattern>
In each example, the first composition shown in the table was applied onto a silicon wafer by spin coating and dried on a hot plate at 100° C. for 5 minutes to form a first photosensitive layer (first photosensitive film) having a uniform thickness of 20 μm on the silicon wafer.
The first photosensitive layer was irradiated with ultraviolet light at 400 mJ/ ^cm2 through a photomask having a trench pattern (each pitch dimension is 8 times each trench dimension) with dimensions for dimensions from 5 μm to 25 μm in 1 μm increments (first exposure step). The first photosensitive layer after exposure was developed using cyclopentanone and rinsed using PGMEA to form a first pattern (first development step).
After development, the second composition shown in the table was applied by spin coating onto the first pattern and onto the area where the first pattern had been removed by the first development step, and dried on a hot plate at 100° C. for 5 minutes to form a second photosensitive layer (second photosensitive film) with a uniform thickness of 20 μm.
The second photosensitive layer was irradiated with ultraviolet light at 400 mJ/cm ² through the photomask so as to overlap with the exposed region of the first photosensitive layer (second exposure step). The exposed second photosensitive layer was developed using cyclopentanone and rinsed using PGMEA to form a second pattern (second development step).
In addition, in the examples in which the composition is described in the "Third resin composition" column, a third pattern was formed on the second pattern by a method similar to that for forming the second pattern.
Thereafter, the first pattern and the second pattern were heated in a heating furnace at the heating temperature and for the heating time shown in the "Cure Conditions" column in the table (modification step) to obtain a composite pattern.
In Comparative Example 1, a pattern was formed in the same manner as in the Example, except that only the first pattern was formed and the second pattern was not formed.
In Comparative Example 2, a composite pattern was formed in the same manner as in Example, except that the modification step was carried out after each of the first and second development steps.

<Measurement of Cyclization Rate>
The cyclization rate was determined by measuring the first pattern (the pattern derived from the first photosensitive composition) by infrared absorption spectroscopy after each of the first and second development steps, and calculating the cyclization rate of the resin A contained in the first pattern.
First, after patterning the first photosensitive composition, the cyclization rate of resin A in the first pattern after the first development step (cyclization rate 1) was measured by infrared absorption spectroscopy. Then, after patterning the second photosensitive composition, the cyclization rate of resin A in the first pattern after the second development step (cyclization rate 2) was measured by infrared absorption spectroscopy for a portion where the pattern of the second photosensitive composition did not remain and the pattern of the first photosensitive composition remained.
When the first photosensitive composition contained a polyimide precursor, after patterning of the first photosensitive composition (after the above-mentioned first developing step), a peak intensity P1 near 1377 cm ⁻¹ , which is an absorption peak derived from an imide structure in the first pattern, was obtained. Next, after patterning of the second photosensitive composition (after the above-mentioned second developing step), an infrared absorption spectrum was measured for a portion where the pattern of the second photosensitive composition did not remain but the pattern of the first photosensitive composition remained, and a peak intensity P2 near 1377 cm ⁻¹ was obtained.
Similarly, when the first photosensitive composition was a polybenzoxazole precursor, the peak intensity P1 near 1554 cm ^-1 , which is an absorption peak derived from the benzoxazole structure, was determined. Next, after patterning of the second photosensitive composition, the infrared absorption spectrum of a portion where the pattern of the first photosensitive composition remained but no pattern of the second photosensitive composition remained was measured, and the peak intensity P2 near 1554 cm ^-1 was determined.
For each resin, the cyclization rate was calculated based on the obtained peak intensities P1 and P2 according to the following formula: The results are shown in the "Cyclization rate" column in the table below.
Cyclization rate (%) = (peak intensity P2/peak intensity P1) x 100
In the table, the notation "<1.1" means that the above ratio is less than 1.1, and the notation ">1.5" means that the above ratio is greater than 1.5.

<Measurement of remaining film rate>
After the first pattern was formed and after the second pattern was formed, the residual film rate in the first pattern was measured using cross-sectional SEM (cross-sectional observation with a scanning electron microscope).
The height of the pattern after the first pattern was formed was designated as T1, and the height of the first pattern after the second pattern was formed was designated as T2, and the remaining film ratio was calculated by the following formula.
Remaining film rate (%) = (T1/T2) x 100
The residual film rate was rated as A when it was 70% or more, and B when it was less than 70%.

<Measurement of dissolution rate ratio>
After preparing the first and second photosensitive films, the dissolution rates were measured using an RDA-790 manufactured by LithoTech Japan. Cyclopentanone was used for the solvent development, and a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution was used for the alkali development. The dissolution rate of the first photosensitive film was R1, and the dissolution rate of the second photosensitive film was R2, and the dissolution rate ratio was calculated using the following formula.
Dissolution rate ratio=(R2/R1) The evaluation results are shown in the "Dissolution rate ratio" column in the table.
・When the dissolution rate ratio is 1.05 or more, it is indicated as A.
- When the dissolution rate ratio was less than 1.05 and 1.0 or more, it was indicated as B. - When the dissolution rate ratio was less than 1.0, it was indicated as C.

<Aspect ratio measurement>
The aspect ratio was measured by a cross-sectional SEM. The total remaining film (pattern height) after patterning of the first, second or third photosensitive composition was defined as T3, and the minimum line width of the trench or contact hole obtained at that time was defined as D1, and the aspect ratio was calculated by the following formula.
Aspect ratio = T3/D1
From the calculated aspect ratio, evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "Aspect Ratio" column in the table.
-Evaluation criteria-
If the aspect ratio is 9 or more, then S
A is when the aspect ratio is less than 9 and greater than or equal to 6.
B: aspect ratio is less than 6 to 4.5 or more;
C: aspect ratio is less than 4.5 to 3 or more;
The aspect ratio of less than 3 was rated D.

From the above results, it can be seen that the composite pattern manufacturing method of the present invention can produce composite patterns with high aspect ratios.

<Example 101>
The first resin composition used in Example 3 was applied in a layer form by spin coating to the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed, and dried on a hot plate at 100° C. for 300 seconds to form a first photosensitive film. The film thickness was set to a film thickness that would result in a film thickness of 24 μm after drying. The first photosensitive film was then exposed using a stepper (CANON FPA3000 i5). The exposure was performed at a wavelength of 365 nm through a mask on which a trench pattern with a size closest to 5 μm was formed in the above-mentioned example. After exposure, the film was heated at 120° C. for 300 seconds. After the above heating, the film was developed with cyclopentanone and rinsed with PGMEA to obtain a first pattern.
Thereafter, the second resin composition used in Example 1 was applied by spin coating onto the first pattern and onto the area where the first pattern had been removed by the first development step, and dried on a hot plate at 100° C. for 300 seconds to form a second photosensitive film. The film thickness after drying was 24 μm.
Thereafter, the second photosensitive film was exposed and developed in the same manner as the first photosensitive film to obtain a second pattern.
Next, the temperature was increased at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 240° C., the temperature was maintained for 30 minutes to harden the first pattern and the second pattern, thereby forming an interlayer insulating film for a rewiring layer made of a composite pattern. This interlayer insulating film for a rewiring layer had excellent insulating properties.
Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, it was confirmed that they operated without any problems.

Claims (12)

a first film-forming step of applying a first resin composition onto a substrate to form a first photosensitive film;
a first exposure step of selectively exposing the first photosensitive film;
a first development step of developing the first photosensitive film after exposure to form a first pattern , the development being a development in which non-exposed portions of the film are developed and removed ;
a second film forming step of applying a second resin composition onto the first pattern and onto the area where the first pattern has been removed by the first developing step to form a second photosensitive film;
a second exposure step of selectively exposing the second photosensitive film;
a second development step of developing the exposed second photosensitive film to form a second pattern, the second development being a development in which non-exposed portions of the film are developed away ; and
A modification step of modifying the first pattern and the second pattern at the same time,
The first resin composition comprises a resin A,
the resin A is at least one selected from the group consisting of a polyimide precursor, a polyimide precursor having a polyimide structure, a polybenzoxazole precursor, a polybenzoxazole precursor having a polybenzoxazole structure, a polyamideimide precursor, and a polyamideimide precursor having a polyamideimide structure;
The second resin composition comprises a resin B,
a ratio S2/S1 of a dissolution rate S1 of the first photosensitive film in a developer in a first development step to a dissolution rate S2 of the second photosensitive film in a developer in a second development step is 1.05 or more;
The denaturing step is a heating step in which the first pattern and the second pattern are heated at the same time.
A method for manufacturing a composite pattern. The method for producing a composite pattern according to claim 1, wherein the resin A has a polymerizable group. The method for producing a composite pattern according to claim 1 or 2, wherein the ratio of the cyclization rate of the resin A in the first pattern after the second development step to the cyclization rate of the resin A in the first pattern after the first development step is 1.1 times or less. The method for producing a composite pattern according to any one of claims 1 to 3, wherein the first resin composition contains a polymerizable compound. The method for producing a composite pattern according to claim 4, wherein the first resin composition contains a polymerizable compound having three or more functionalities as the polymerizable compound. The method for producing a composite pattern according to any one of claims 1 to 5, wherein the resin B is at least one selected from the group consisting of a polyimide precursor, a polyimide precursor having a polyimide structure, a polybenzoxazole precursor, a polybenzoxazole precursor having a polybenzoxazole structure, a polyamideimide precursor, a polyamideimide precursor having a polyamideimide structure, and an epoxy resin. 7. The method for producing a composite pattern according to claim 1 , wherein a remaining film ratio of the first pattern to which the second developing step has been applied is 70% or more. The method for producing a composite pattern according to any one of claims 1 to 7 , wherein the first resin composition does not contain a colorant. The method for producing a composite pattern according to any one of claims 1 to 8 , wherein the resin A and the resin B are resins containing repeating units represented by the same structural formula. The method includes a step of applying the method for producing a composite pattern according to any one of claims 1 to 9 multiple times.
A method for manufacturing a laminate. The method for producing a laminate according to claim 10 , further comprising a metal layer forming step of forming a metal layer on a layer consisting of the composite pattern, the metal layer forming step being included between steps of applying the method for producing the composite pattern a plurality of times. A method for producing a semiconductor device, comprising the method for producing a composite pattern according to any one of claims 1 to 9 , or the method for producing a laminate according to claim 10 or 11 .