JP7627700B2 - Method for producing cured product, resin composition, developer, method for producing laminate, and method for producing semiconductor device - Google Patents

Description

The present invention relates to a method for producing a cured product, a resin composition, a developer, a method for producing a laminate, and a method for producing a semiconductor device.

Resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulating properties. Although the above applications are not particularly limited, taking semiconductor devices for mounting as an example, patterns containing these resins can be used as insulating films, sealing materials, or protective films. Patterns containing these resins are also used as base films and coverlays for flexible substrates.

For example, in the above-mentioned applications, a resin such as polyimide is used in the form of a resin composition containing a polyimide precursor.
Such a resin composition can be applied to a substrate by, for example, coating, and then, if necessary, exposed to light, developed, modified, or the like, to form a cured product of the polyimide precursor on the substrate.
The resin composition can be applied by known coating methods and can form fine patterns, patterns with complex shapes, and the like by development, and therefore has a high degree of freedom in designing the cured film, 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 polyimides and the like, 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.

For example, Patent Document 1 describes a method for producing a relief pattern, which includes a step of forming a coating film or a molded body using a negative photosensitive resin composition, irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern, and then heating the coating film or the molded body before a development step in which unexposed portions of the coating are removed to form a pattern, characterized in that the heating step is a step of heating the coating film or the molded body via a heat medium or by radiation of electromagnetic waves in an atmosphere in which gas is actively and continuously supplied from outside the system and volatile components generated from the coating film or the molded body are actively removed outside the system.

JP 2011-227485 A

In conventional manufacturing methods for cured products, there is a demand for improving resolution.

The present invention aims to provide a method for producing a cured product having excellent resolution, a resin composition used in the method for producing the cured product, a developer used in the method for producing the cured product, a method for producing a laminate including the method for producing the cured product, and a method for producing an electronic device including the method for producing the cured product or the method for producing the laminate.

上記式（１）中、Ｒ^１は、４価の有機基を表す；複数のＲ^１は互いに同一であっても異なっていてもよい；Ｒ^２は、２価の有機基を表す；複数のＲ^２は互いに同一であっても異なっていてもよい；Ｒ^３は、各々独立に、水素原子又は有機基を表す。
＜４＞ 上記式（１）で表される繰り返し単位が上記酸の作用により極性が増大する反応を生じる基を有する、＜３＞に記載の硬化物の製造方法。
＜５＞ 上記樹脂組成物が酸捕捉剤を更に含む、＜１＞～＜４＞のいずれか１つに記載の硬化物の製造方法。
＜６＞ 上記現像液が、ハンセン溶解度パラメータの水素結合項ｄＨの値が８以下である有機溶剤を８０質量％以上含む、＜１＞～＜５＞のいずれか１つに記載の硬化物の製造方法。
＜７＞ 上記酸の作用により極性が増大する反応を生じる基が下記式（Ａ－１）又は下記式（Ａ－２）で表される基である、＜１＞～＜６＞のいずれか１つに記載の硬化物の製造方法。

式（Ａ－１）中、Ｒ^Ａ１～Ｒ^Ａ５はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^Ａ１～Ｒ^Ａ５のうち少なくとも２つが結合して環構造を形成していてもよく、＊は他の構造との結合部位を表す；
式（Ａ－２）中、Ｒ^Ａ６～Ｒ^Ａ８はそれぞれ独立に、１価の有機基を表し、Ｒ^Ａ６～Ｒ^Ａ８のうち少なくとも２つが結合して環構造を形成していてもよく、＊は他の構造との結合部位を表す。
＜８＞ 上記変性工程において、上記パターンの加熱が行われる、＜１＞～＜７＞のいずれか１つに記載の硬化物の製造方法。
＜９＞ 上記露光工程後、上記現像工程前に、上記膜を加熱する工程を更に含む、＜１＞～＜８＞のいずれか１つに記載の硬化物の製造方法。
＜１０＞ ＜１＞～＜９＞のいずれか１つに記載の硬化物の製造方法を複数回繰り返すことを含む
積層体の製造方法。
＜１１＞ 複数回行われる硬化物の製造方法の間に、硬化物からなる層上に金属層を形成する金属層形成工程を更に含む、＜１０＞に記載の積層体の製造方法。
＜１２＞ ＜１＞～＜９＞のいずれか１つに記載の硬化物の製造方法、又は、＜１０＞若しくは＜１１＞に記載の積層体の製造方法を含む、
電子デバイスの製造方法。
＜１３＞ ＜１＞～＜９＞のいずれか１つに記載の硬化物の製造方法に用いられる樹脂組成物。
＜１４＞ ＜１＞～＜９＞のいずれか１つに記載の硬化物の製造方法に用いられる現像液。 Examples of typical embodiments of the present invention are given below.
<1> A film-forming step of applying a resin composition containing a resin, a compound that generates an acid upon irradiation with actinic rays or radiation, and a solvent onto a substrate to form a film;
an exposure step of selectively exposing the film to light;
a developing step of developing the exposed film with a developer to form a pattern; and
A modification step of modifying the pattern,
the resin is a polyimide precursor,
The resin has a group that undergoes a reaction to increase polarity by the action of an acid,
The content of the organic solvent in the developer is 80% by mass or more based on the total mass of the developer,
The modification reduces the solubility of the pattern in a solvent contained in the resin composition.
A method for producing a cured product.
<2> The method for producing a cured product according to <1>, wherein the obtained cured product has a film thickness of 5 μm or more. <3> The method for producing a cured product according to <1> or <2>, wherein the resin contains a repeating unit represented by the following formula (1):

In the above formula (1), R ¹ represents a tetravalent organic group; multiple R ^1s may be the same or different; R ² represents a divalent organic group; multiple R ^2s may be the same or different; and each R ³ independently represents a hydrogen atom or an organic group.
<4> The method for producing a cured product according to <3>, wherein the repeating unit represented by formula (1) has a group that undergoes a reaction to increase polarity by the action of the acid.
<5> The method for producing a cured product according to any one of <1> to <4>, wherein the resin composition further contains an acid scavenger.
<6> The method for producing a cured product according to any one of <1> to <5>, wherein the developer contains 80% by mass or more of an organic solvent having a value of the hydrogen bond term dH of the Hansen solubility parameters of 8 or less.
<7> The method for producing a cured product according to any one of <1> to <6>, wherein the group that undergoes a reaction to increase polarity by the action of an acid is a group represented by the following formula (A-1) or the following formula (A-2):

In formula (A-1), R ^A1 to R ^A5 each independently represent a hydrogen atom or a monovalent organic group, at least two of R ^A1 to R ^A5 may be bonded to form a ring structure, and * represents a bonding site to another structure;
In formula (A-2), R ^A6 to R ^A8 each independently represent a monovalent organic group, at least two of R ^A6 to R ^A8 may be bonded to form a ring structure, and * represents a bonding site to another structure.
<8> The method for producing a cured product according to any one of <1> to <7>, wherein the modification step includes heating the pattern.
<9> The method for producing a cured product according to any one of <1> to <8>, further comprising a step of heating the film after the exposure step and before the development step.
<10> A method for producing a laminate, comprising repeating the method for producing a cured product according to any one of <1> to <9> multiple times.
<11> The method for producing a laminate according to <10>, further comprising a metal layer forming step of forming a metal layer on a layer made of the cured product, between the processes for producing the cured product which are performed a plurality of times.
<12> A method for producing a cured product according to any one of <1> to <9>, or a method for producing a laminate according to <10> or <11>,
A method for manufacturing an electronic device.
<13> A resin composition used in the method for producing a cured product according to any one of <1> to <9>.
<14> A developer used in the method for producing a cured product according to any one of <1> to <9>.

The present invention provides a method for producing a cured product having excellent resolution, a resin composition used in the method for producing the cured product, a developer used in the method for producing the cured product, a method for producing a laminate including the method for producing the cured product, and a method for producing an electronic device including the method for producing the cured product 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 for producing the cured product)
The method for producing a cured product of the present invention includes a film formation step of applying a resin composition containing a resin, a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as a "photoacid generator"), and a solvent onto a substrate to form a film, an exposure step of exposing the film to a pattern using actinic rays or radiation, a development step of developing the exposed film with a developer to obtain a pattern, and a modification step of modifying the pattern, wherein the resin is a polyimide precursor, the resin has a group that undergoes a reaction to increase polarity under the action of an acid (hereinafter also referred to as a "polarity conversion group"), the content of the organic solvent relative to the total mass of the developer is 80 mass% or more, and the modification reduces the solubility of the pattern in the solvent contained in the resin composition.
Hereinafter, in the present invention, the resin which is a polyimide precursor and has a polarity conversion group is also referred to as a "specific resin".
According to the method for producing a cured product of the present invention, a cured product having excellent resolution can be obtained.
The mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.

A negative pattern can be formed by using a film formed from a resin composition containing a polyimide precursor having a polarity conversion group and a photoacid generator, and by using a developer having an organic solvent content of 80 mass % or more.
A negative pattern refers to a pattern in which the unexposed areas of the film are removed in the development step.
Specifically, in the exposure step, an acid is generated from the photoacid generator in the exposed area, and the polarity of the polarity conversion group of the resin increases due to the action of the acid, so that the solubility of the resin in the developer in the exposed area decreases, and after the development step, the exposed area remains and the unexposed area is removed.
Here, it is believed that the increase in polarity suppresses the intrusion of the developer into the exposed area, thereby suppressing swelling of the resulting pattern due to the developer.
It is believed that by suppressing the swelling, when a hole pattern is to be formed, for example, a hole pattern with open holes can be easily obtained even in a fine hole pattern.
Furthermore, by suppressing the swelling, when forming a line pattern, for example, it is believed that swelling of the line portion is suppressed, making it easier to form a finer line pattern.
In other words, according to the method for producing a cured product of the present invention, it is possible to form a fine pattern and the resolution is excellent.
Furthermore, since the composition of the present invention is modified such that its solubility in a solvent contained in the resin composition is reduced, even when another resin composition is applied onto the resulting pattern to form a laminate structure, it is presumed that the pattern is less likely to dissolve in the resin composition, the dimensional stability of the first layer pattern upon lamination is excellent, and the resolution of the second layer pattern upon lamination is excellent, resulting in excellent formability of the laminate pattern.

Here, Patent Document 1 does not disclose the use of a film formed from a resin composition containing a polyimide precursor having a polarity conversion group and a photoacid generator, nor does it disclose the use of a developer having an organic solvent content of 80 mass % or more.
The method for producing the cured product of the present invention will now be described in detail.

<Film formation process>
The method for producing a cured product of the present invention includes a film formation step of applying a resin composition containing a resin, a compound that generates an acid upon irradiation with actinic rays or radiation, and a solvent onto a substrate to form a film.
The 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 limited. In the present invention, semiconductor preparation 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 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 the preferred means for applying the resin composition of the present invention onto a 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 of the resin composition and the coating conditions 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.
Furthermore, a pre-wetting step may be employed in which, before applying the resin composition to the substrate, the substrate is coated with various solvents to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process>
After the film-forming step (layer-forming step), the above-mentioned film may be subjected to a step of drying the formed film (layer) (drying step) in order to remove the solvent.
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
The drying step is preferably carried out after the film-forming step and before the exposure step.
The drying temperature of the film in the 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.

<Exposure process>
The film is subjected to an exposure step to selectively expose the film to light.
That is, the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film formed in the film formation step to light.
Selective exposure means that only a portion of the film is exposed, and selective exposure results in exposed and unexposed areas of the film.
The amount of exposure light is not particularly limited as long as it is capable of curing the resin composition of the present invention. For example, the amount of exposure light 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 (wavelengths 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 resin composition of the present invention, 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 that exposes at least a portion of the film made of the resin composition of the present invention, and examples of the exposure method include exposure using a photomask and exposure by a laser direct imaging method.

<Post-exposure baking process>
The film may be subjected to a step of heating after exposure (post-exposure baking step).
That is, the method for producing a cured product of the present invention may include a post-exposure baking step of heating the film exposed in the exposure step.
The post-exposure baking step can be carried out after the exposure step and before the development step.
The heating temperature in the 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 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 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.
It is also preferable to carry out heating using a hot plate, oven, or the like that is set to the desired temperature.
The heating means in the post-exposure baking step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. 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.

<Developing process>
After exposure, the film is subjected to a development step in which it is developed with a developer to form a pattern.
That is, the method for producing a cured product of the present invention includes a development step in which the film exposed in the exposure step is developed with a developer to form a pattern.
By developing, the unexposed areas of the film are removed to form the pattern.
Here, development in which the non-exposed portion of the film is removed by the development process is called negative development, and development in which the exposed portion of the film is removed by the development process is called positive development.

[Developer]
The developer used in the method for producing a cured film of the present invention has an organic solvent content of 80 mass % or more based on the total mass of the developer.

- Organic solvents -
The developer preferably contains an organic solvent in an amount of 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on the total mass of the developer. The upper limit of the content of the organic solvent is not particularly limited and may be 100% by mass.
The developer preferably contains 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 98% by mass or more of an organic solvent having a hydrogen bond term dH value of the Hansen solubility parameters of 8 or less. The upper limit of the content of the organic solvent having a dH value of 8 or less is not particularly limited, and may be 100% by mass.
The hydrogen bond term dH of the Hansen solubility parameter in an organic solvent is a value calculated using the Hansen Solubility Parameter Software (HSPiP).

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.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, methyl 3-methoxypropionate, etc.)), ethyl cypropionate, 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.), methyl pyruvate, pyruvate 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, and 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.

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 development process, a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate by ultrasonic waves or the like, or a combination of these processes can be used.

The development time is preferably 10 seconds to 10 minutes, and 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, and more preferably 18°C to 30°C.

In the development process, after the treatment with the developer, the pattern may be washed (rinsed) with a rinse solution. Alternatively, a rinse solution may be supplied before the developer in contact with the pattern has 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 the desired pattern can be formed, and examples of the method include a method of immersing the substrate in the rinse liquid, paddle development on the substrate, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the developer 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.

<Modification step>
The method for producing a cured product of the present invention includes a modification step of modifying the above-mentioned pattern (the pattern obtained in the development step).
The modification step is preferably a step of imidizing the polyimide precursor within the pattern.
In the modification step, the pattern is preferably heated.
That is, the modification step is preferably a step of imidizing the polyimide precursor within the pattern by heating.
The heating is preferably carried out by the method described in the heating step below.

<Heating process>
The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step.
The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without carrying out a development step, or a film obtained in a film formation step.
In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide.
Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in the crosslinking agent other than the specific resin also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

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 of the cured product.
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 which the process of heating to the maximum heating temperature begins. For example, when the resin composition of the present invention is applied to a substrate and then dried, it is the temperature of the film (layer) after drying, and it is preferable to raise the temperature from a temperature that is 30 to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

The heating time (heating time at the highest 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 step>
The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light, in addition to the above-mentioned heating step.
That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure 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 part of the pattern obtained in the development step is exposed, but it is preferable that the entire 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.

<Metal Layer Forming Process>
The pattern obtained by the development step (preferably subjected to at least one of the heating step and the post-exposure development step) may be subjected to a metal layer formation step in which a metal layer is formed on the pattern.
That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained in the development step (preferably subjected to a heating 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 the cured product of the present invention or the field in which the cured product of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. In addition, examples include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), and the formation of patterns by etching of 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 Polyimides" 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 Polyimides Basics and Applications" NTS, August 2010, etc.

The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used in the production of printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for the production of protective lacquers and dielectric layers in electronics, especially microelectronics.

The thickness of the cured product obtained by the method for producing a cured product of the present invention is preferably 5 μm or more, more preferably 10 μm or more, more preferably 15 μm or more, and particularly preferably 20 μm or more, from the viewpoint of, for example, the insulating properties of the cured product. The upper limit of the thickness is not particularly limited, but can be, for example, 50 μm or less.
According to the method for producing a cured product of the present invention, a cured product having excellent resolution can be produced even in the case of such a relatively thick film.

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

That is, the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.

The laminate of the present invention preferably includes two or more layers made of a cured product, and includes a metal layer between any two of the layers made of the cured product. 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 made of a cured product between the steps for producing a cured product which are performed multiple times. A preferred embodiment of the metal layer forming step is as described above.
As the laminate, for example, a laminate having at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example.
The layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or 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 process is a series of processes including (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process, which are carried out again on the surface of the pattern (resin layer) or metal layer in this order. However, the film formation process (a) and the heating process (d) may be repeated. In addition, the heating process (d) may be followed by the metal layer formation process (e). It goes without saying that the lamination process may further include the drying process and the like as appropriate.

If a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or 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 structure of 2 to 20 resin layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
The layers may be the same or different in composition, shape, film thickness, etc.

In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specifically, the steps may be repeated in the order of (a) film formation step, (b) exposure step, (c) development step, (d) heating step, and (e) metal layer formation step, or the steps may be repeated in the order of (a) film formation step, (d) heating step, and (e) metal layer formation step. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention 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 subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
The surface activation treatment step is usually carried out after the metal layer forming step, but after the heating step, the resin composition layer may be subjected to the surface activation treatment step before the metal layer forming 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 resin composition layer after heating, or on at least a part of both the metal layer and the resin composition layer after heating. 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 resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved.
In addition, it is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been surface-activated. In particular, when performing negative development, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the 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 Electronic Devices)
The present invention also discloses a method for producing a semiconductor device, including the method for producing the cured product of the present invention or the method for producing the laminate of the present invention. Specific examples of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

(Resin composition)
The resin composition of the present invention is a resin composition used in the method for producing a cured product of the present invention.
The resin composition of the present invention comprises a resin, a compound that generates an acid when irradiated with actinic rays or radiation, and a solvent, wherein the resin is a polyimide precursor, and the resin has a group that undergoes a reaction in which the polarity increases under the action of an acid.
Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<Resin>
The resin composition is a polyimide precursor, and contains a resin having a group (polarity conversion group) that undergoes a reaction to increase polarity under the action of an acid.
The polarity conversion group may be an acid-decomposable group, and is preferably a group that decomposes under the action of an acid to generate an alkali-soluble group.
Examples of the acid-decomposable group include an acetal group, a silyl group, a silyl ether group, and a tertiary alkyl ester group. Of these, an acetal group or a tertiary alkyl ester group is preferred, and from the viewpoint of exposure sensitivity, an acetal group is more preferred.

式（Ａ－１）中、Ｒ^Ａ１～Ｒ^Ａ５はそれぞれ独立に、水素原子又は１価の有機基を表し、Ｒ^Ａ１～Ｒ^Ａ５のうち少なくとも２つが結合して環構造を形成していてもよく、＊は他の構造との結合部位を表す；
式（Ａ－２）中、Ｒ^Ａ６～Ｒ^Ａ８はそれぞれ独立に、１価の有機基を表し、Ｒ^Ａ６～Ｒ^Ａ８のうち少なくとも２つが結合して環構造を形成していてもよく、＊は他の構造との結合部位を表す。 Among these, the polarity conversion group is preferably a group represented by the following formula (A-1) or (A-2).

In formula (A-1), R ^A1 to R ^A5 each independently represent a hydrogen atom or a monovalent organic group, at least two of R ^A1 to R ^A5 may be bonded to form a ring structure, and * represents a bonding site to another structure;
In formula (A-2), R ^A6 to R ^A8 each independently represent a monovalent organic group, at least two of R ^A6 to R ^A8 may be bonded to form a ring structure, and * represents a bonding site to another structure.

In formula (A-1), R ^A1 and R ^A2 each independently represent a hydrogen atom or a monovalent organic group, and are preferably a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic polyvalent hydrogen group, or a group represented by a bond between them, but is preferably an aliphatic hydrocarbon group or a group represented by a bond between an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and is preferably a saturated aliphatic hydrocarbon group or a group represented by a bond between a saturated aliphatic hydrocarbon group and an aromatic hydrocarbon group.
In formula (A-1), R ^A3 to R ^A5 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent hydrocarbon group, and more preferably a hydrogen atom.
In addition, in formula (A-1), when at least two of R ^A1 to R ^A5 are bonded to form a ring structure, it is preferable that at least one of R ^A1 and R ^A2 is bonded to at least one of R ^A3 to R ^A5 to form a ring structure. Examples of the ring structure formed include a tetrahydrofuran ring.
In formula (A-2), ^R to ^R each independently represent a monovalent organic group, preferably a monovalent hydrocarbon group, more preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, even more preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When at least two of R ^A6 to R ^A8 combine to form a ring structure, the ring structure is not particularly limited, but is preferably an aliphatic hydrocarbon ring structure, and more preferably a saturated aliphatic hydrocarbon ring structure.

[Polyimide precursor]
The polyimide precursor used in the present invention preferably contains a repeating unit represented by the following formula (1).

In the above formula (1),
R ¹ represents a tetravalent organic group. A plurality of R ¹ may be the same or different.
^R2 represents a divalent organic group. A plurality of ^R2 may be the same or different.
Each ^R3 independently represents a hydrogen atom or an organic group.
The repeating unit represented by formula (1) preferably contains a polarity conversion group, more preferably at least one of the multiple -CO ₂ R ³ in formula (1) is a group containing a polarity conversion group, and further preferably at least one of the multiple -CO ₂ R ³ in formula (1) is a group that decomposes under the action of an acid to generate an alkali-soluble group.

式（Ａ’－１）中、Ｒ^Ａ１～Ｒ^Ａ５はそれぞれ、式（Ａ－１）中のＲ^Ａ１～Ｒ^Ａ５と同義であり、好ましい態様も同様である。また、＊は式（１）中のＲ^３が結合する酸素原子との結合部位を表す。
式（Ａ’－２）中、Ｒ^Ａ６～Ｒ^Ａ８はそれぞれ、式（Ａ－２）中のＲ^Ａ６～Ｒ^Ａ８と同義であり、好ましい態様も同様である。また、＊は式（１）中のＲ^３が結合する酸素原子との結合部位を表す。 The repeating unit represented by the above formula (1) preferably contains a group represented by the above formula (A-1) or formula (A-2).
When the repeating unit represented by formula (1) contains a group represented by formula (A-1) above, it is preferable that R ³ in formula (1) is a group represented by formula (A'-1) below, so that the repeating unit represented by formula (1) contains a group represented by formula (A-1) above.
In addition, when the repeating unit represented by formula (1) contains a group represented by the above formula (A-2), it is preferable that R ³ in formula (1) is the following formula (A'-2), so that the repeating unit represented by formula (1) contains a group represented by the above formula (A-2).

In formula (A'-1), ^R to ^R have the same meanings as ^R to ^R in formula (A-1), and preferred embodiments are also the same. Also, * represents the bonding site with the oxygen atom to which ^R in formula (1) is bonded.
In formula (A'-2), ^R to ^R have the same meanings as ^R to ^R in formula (A-2), and preferred embodiments are also the same. Also, * represents the bonding site with the oxygen atom to which ^R in formula (1) is bonded.

A resin having a repeating unit represented by formula (1) is a resin whose solubility in an alkaline developer increases under the action of an acid. A resin having a repeating unit of formula (1) is preferably insoluble or poorly soluble in an alkaline developer.

The repeating unit represented by formula (1) is composed of an acid component derived from a compound having four carboxy groups with ^R1 as the nucleus, a carboxylic acid anhydride thereof, or a compound in which the hydrogen atom in at least one of the four carboxy groups is substituted with a group that is eliminated by the action of an acid, and a diamine component derived from a compound having two amino groups with ^R2 as the nucleus. In other words, it is composed of an acid component which is a partial structure containing the two carbonyl groups sandwiched between the two carbonyl groups in formula (1), and a diamine component which is a partial structure represented by -NH- ^R2 -NH- in formula (1).
The tetravalent organic group R ¹ preferably has 4 to 30 carbon atoms and is more preferably a tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group. Multiple R ^1s may be the same or different.
Examples of the monocyclic aromatic group in the tetravalent organic group R ¹ include a benzene ring group and a pyridine ring group.
Examples of the condensed polycyclic aromatic group in the tetravalent organic group R ¹ include a naphthalene ring group and a perylene ring group.
Examples of the monocyclic aliphatic group in the tetravalent organic group R ¹ include a cyclobutane ring group, a cyclopentane ring group, and a cyclohexane ring group.
Examples of the condensed polycyclic aliphatic group in the tetravalent organic group R ¹ include a bicyclo[2.2.1]heptane ring group, a bicyclo[2.2.2]octane ring group, and a bicyclo[2.2.2]oct-7-ene ring group.
The tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group for the tetravalent organic group ^R1 may be the above-mentioned monocyclic or condensed polycyclic aliphatic group or aromatic group itself, or a plurality of monocyclic or condensed polycyclic aliphatic groups or aromatic groups may be linked via a single bond or a divalent linking group to form a tetravalent linking group as ^R1 .
Examples of the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, or a propylene group), an oxygen atom, a sulfur atom, a divalent sulfone group, an ester bond, a ketone group, or an amide group.

Specific examples of the acid component having at least four groups derived from a carboxy group with R ¹ as the nucleus include pyromellitic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2,3,3',4'-biphenyltetracarboxylic anhydride, 2,2',3,3'-biphenyltetracarboxylic anhydride, 3,3',4,4'-benzophenonetetracarboxylic anhydride, 2,2',3,3'-benzophenonetetracarboxylic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3,5,6-pyridinetetracarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic anhydride, (trifluoromethyl)pyromellitic anhydride, di(trifluoromethyl) Pyromellitic anhydride, di(heptafluoropropyl)pyromellitic anhydride, pentafluoroethylpyromellitic anhydride, bis[3,5-di(trifluoromethyl)phenoxy]pyromellitic anhydride, 3,3',4,4'-tetracarboxydiphenyl ether dianhydride, 2,3',3,4'-tetracarboxydiphenyl ether dianhydride, 3,3',4,4'-tetracarboxydiphenylmethane dianhydride, 3,3',4,4'-tetracarboxydiphenylsulfone dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphenyl dianhydride, 2,2',5,5'-tetrakis(trifluoromethyl) 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphenyl dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxydiphenyl ether dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxybenzophenone dianhydride, bis[(trifluoromethyl)dicarboxyphenoxy]benzene dianhydride, bis(dicarboxyphenoxy)bis(trifluoromethyl)benzene dianhydride, bis(dicarboxyphenoxy)tetrakis(trifluoromethyl)benzene dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 5,5'-[p-phenylenebis(oxycarbonyl ) ] diphthalic anhydride, and other aromatic tetracarboxylic anhydrides, and components derived from aliphatic tetracarboxylic anhydrides such as cyclobutane tetracarboxylic anhydride, cyclopentane tetracarboxylic anhydride, cyclohexane tetracarboxylic anhydride, 1,2,4,5-cyclohexane tetracarboxylic acid, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, or bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid dianhydride, (1S,2S,4R,5R)-cyclohexane tetracarboxylic dianhydride, and (1R,2S,4S,5R)-cyclohexane tetracarboxylic dianhydride, and other aliphatic tetracarboxylic anhydrides.

Preferably, the component derived from pyromellitic anhydride, the component derived from 3,3',4,4'-biphenyltetracarboxylic anhydride, the component derived from 2,3,3',4'-biphenyltetracarboxylic anhydride, the component derived from 2,2',3,3'-biphenyltetracarboxylic anhydride, the component derived from 3,3',4,4'-benzophenonetetracarboxylic anhydride, the component derived from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, the component derived from 3,3',4,4'-tetracarboxydiphenylether dianhydride, the component derived from 1,2,5,6-naphthalenetetracarboxylic anhydride, the component derived from 5,5'-[p-phenylenebis(oxycarbonyl)]diphthalic anhydride, the component derived from cyclobutanetetracarboxylic anhydride, the component derived from cyclopentanetetracarboxylic anhydride, the component derived from bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride A component derived from (1S,2S,4R,5R)-cyclohexanetetracarboxylic dianhydride, a component derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride, and more preferably a component derived from pyromellitic anhydride, a component derived from 3,3',4,4'-biphenyltetracarboxylic anhydride, a component derived from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, a component derived from cyclobutanetetracarboxylic anhydride, a component derived from 3,3',4,4'-tetracarboxydiphenylether dianhydride, a component derived from cyclopentanetetracarboxylic anhydride, a component derived from 5,5'-[p-phenylenebis(oxycarbonyl)]diphthalic anhydride, a component derived from (1S,2S,4R,5R)-cyclohexanetetracarboxylic dianhydride, and a component derived from (1R,2S,4S,5R)-cyclohexanetetracarboxylic dianhydride. By using these, good solvent solubility, alkali dissolution rate, transparency, and stress characteristics can be realized.
The content of the acid component derived from a compound having four carboxy groups with ^R1 as a nucleus in the resin is preferably 20 to 70 mol %, and more preferably 30 to 60 mol %, based on all repeating units constituting the resin.

R ² in formula (1) 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, each Ar is 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 group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

^R2 is preferably derived from a diamine. Examples of the diamine used in the production of the resin include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one diamine may be used, or two or more diamines 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.

式中、Ａは単結合又は２価の連結基を表し、単結合、又は、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－ＳＯ_２－、ＮＨＣＯ－、又は、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、又は、－ＳＯ_２－から選択される基であることがより好ましく、－ＣＨ_２－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－Ｃ（ＣＦ_３）_２－、又は、－Ｃ（ＣＨ_３）_２－であることが更に好ましい。
式中、＊は他の構造との結合部位を表す。

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 a combination 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 obtained organic film, ^R2 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 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.

式（５１）中、Ｒ^５０～Ｒ^５７は、それぞれ独立に、水素原子、フッ素原子又は１価の有機基であり、Ｒ^５０～Ｒ^５７の少なくとも１つは、フッ素原子、メチル基又はトリフルオロメチル基である。＊は他の構造との結合部位を表す。
Ｒ^５０～Ｒ^５７の１価の有機基としては、炭素数１～１０（好ましくは炭素数１～６）の無置換のアルキル基、炭素数１～１０（好ましくは炭素数１～６）のフッ化アルキル基等が挙げられる。

式（６１）中、Ｒ^５８及びＲ^５９は、それぞれ独立に、フッ素原子、メチル基、又はトリフルオロメチル基である。＊は他の構造との結合部位を表す。
式（５１）又は（６１）の構造を与えるジアミン化合物としては、２，２’－ジメチルベンジジン、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、２，２’－ビス（フルオロ）－４，４’－ジアミノビフェニル、４，４’－ジアミノオクタフルオロビフェニル等が挙げられる。これらは１種で又は２種以上を組み合わせて用いてもよい。 From the viewpoint of i-line transmittance, ^R2 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, R2 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, and at least one of R ⁵⁰ to R ⁵⁷ represents a fluorine atom, a methyl group, or a trifluoromethyl group. * represents a bonding site to another structure.
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. * represents a bonding site to another structure.
Examples of the diamine compound that gives 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 order to enhance adhesion to the substrate, a silicon diamine component may be used as the diamine component having ^R2 as a nucleus. Examples of such a diamine component include a bis(4-aminophenyl)dimethylsilane component, a bis(4-aminophenyl)tetramethylsiloxane component, a bis(4-aminophenyl)tetramethyldisiloxane component, a bis(γ-aminopropyl)tetramethyldisiloxane component, a 1,4-bis(γ-aminopropyldimethylsilyl)benzene component, a bis(4-aminobutyl)tetramethyldisiloxane component, and a bis(γ-aminopropyl)tetraphenyldisiloxane component.
The silicon diamine component may also have the following structure:

In the above formula, _R5 and _R6 represent a divalent organic group, and _R7 and _R8 each independently represent a monovalent organic group. That is, multiple _R7s may be the same or different from each other. Multiple _R8s may be the same or different from each other.
The divalent organic group represented by _R5 and _R6 represents a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, a phenylene group having 6 to 20 carbon atoms, a divalent alicyclic group having 3 to 20 carbon atoms, or a group formed by combining these.
The monovalent organic group represented by R ₇ and R ₈ represents a linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent, or an aryl group having 6 to 20 carbon atoms.
More specifically, the following can be mentioned:

In the specific resin, at least one of the multiple _{--CO.sub.2R.sub.3} ^groups present in the resin is preferably a group that decomposes under the action of an acid to generate an alkali-soluble group.
The group that decomposes under the action of an acid to generate an alkali-soluble group refers to a group that decomposes under the action of an acid to generate an alkali-soluble group such as a hydroxy group (e.g., a phenolic hydroxy group) or a carboxy group on the resin side (hereinafter also referred to as an acid-decomposable group). In the present invention, the acid-decomposable group is preferably a group that decomposes under the action of an acid to generate a carboxy group as an alkali-soluble group on the resin side.
Preferred as the acid-decomposable group are groups in which the hydrogen atom of these alkali-soluble groups is substituted with a group which is cleaved by the action of an acid.
Examples of the group that is eliminated by an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ). 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. 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.

The acid-decomposable group is preferably a tertiary alkyl ester group, an acetal ester group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal ester group, and by using these, a photosensitive film with high sensitivity and high resolution can be obtained.

As a tertiary alkyl ester group serving as an acid-decomposable group, it is preferable that the hydrogen atom of the carboxyl group is substituted with a group represented by the following formula (AI):

In formula (AI),
T represents a single bond or *-Rt-COO-# (* is the same as * in formula (AI), and # represents a bonding site with the carbon atom to which Rx ₁ to Rx ₃ are bonded). Rt represents an alkylene group or a cycloalkylene group.
Rx ₁ to Rx ₃ each independently represent a hydrogen atom, an alkyl group (straight-chain or branched), or a cycloalkyl group (monocyclic or polycyclic).
Two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).
* indicates the binding site with other structures.

Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group, or a -(CH ₂ ) ₃ - group.
The alkyl group represented by Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a hexyl group, an octyl group, or a dodecyl group, and more preferably an alkyl group having 1 to 6 carbon atoms.

The cycloalkyl group represented by Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.
The cycloalkyl group formed by combining two of _Rx1 to _Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, etc. A monocyclic cycloalkyl group having 5 or 6 carbon atoms is particularly preferred.
In formula (AI), it is preferable that _Rx1 is a methyl group or an ethyl group, and _Rx2 and _Rx3 are bonded to form the above-mentioned cycloalkyl group.

Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (having 1 to 4 carbon atoms), a polyalkyleneoxy group, a carboxy group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and preferably has 20 or less carbon atoms.

Specific examples of the group represented by formula (AI) constituting the tertiary alkyl ester group as the acid-decomposable group are shown below, but the present invention is not limited thereto.

In the specific examples, Rxa and Rxb each represent an alkyl group having 1 to 6 carbon atoms. Z represents a substituent that each of the above groups may have, and when multiple Zs are present, they are independent of each other. p represents 0 or a positive integer. * represents a bonding site with another structure.

It is more preferable that the tertiary alkyl ester group as the acid-decomposable group is a tertiary alkyl ester group having at least one of a group represented by the following formula (I) and a group represented by the following formula (II) as the group represented by formula (AI).

In formulas (I) and (II), R ₂ , R ₄ , R ₅ and R ₆ each independently represent an alkyl group or a cycloalkyl group.
R represents an atomic group necessary to form an alicyclic structure together with the carbon atom.
* indicates the binding site with other structures.

The alkyl group in _R2 may be linear or branched, and may have a substituent.
The cycloalkyl group for _R2 may be monocyclic or polycyclic and may have a substituent.
_R2 is preferably an alkyl group, more preferably one having 1 to 10 carbon atoms, and even more preferably one having 1 to 5 carbon atoms, such as a methyl group or an ethyl group.

R represents an atomic group necessary to form an alicyclic structure together with the carbon atoms. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and more preferably a hydrocarbon ring structure. The number of carbon atoms in the monocyclic alicyclic structure or hydrocarbon ring structure is preferably 3 to 8, and more preferably 5 or 6.

The alkyl group in R ₄ , R ₅ , and R ₆ may be linear or branched and may have a substituent. The alkyl group is preferably one having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, or a hexyl group.

The cycloalkyl group in _R4 , _R5 , and _R6 may be monocyclic or polycyclic and may have a substituent. As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group is preferable.

Examples of the group represented by formula (I) include groups represented by the following formulas (I-a) and (I-b).

In the formula, _R2 has the same meaning as _R2 in formula (I).
* indicates the binding site with other structures.

It is preferable that the group represented by formula (II) is a group represented by the following formula (II-a):

In formula (II-a),
_R4 and _R5 have the same meanings as in formula (II).
* indicates the binding site with other structures.

Specifically, the acetal ester group as an acid-decomposable group is preferably an ester group in which the hydrogen atom of the carboxy group is substituted with a group represented by the following formula (III).

Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
Rb represents a single bond or a divalent linking group.
Q represents an alkyl group, an alicyclic group which may contain a heteroatom, or an aromatic ring group which may contain a heteroatom.
At least two of Ra, Rb and Q may be bonded to each other to form a ring. This ring is preferably a 5-membered or 6-membered ring.
* indicates the binding site with other structures.

Examples of the alkyl group, cycloalkyl group, aryl group or aralkyl group represented by Ra include the same groups as those mentioned above as the alkyl group, cycloalkyl group, aryl group and aralkyl group for R ₃₆ .
From the viewpoint of suppressing decomposition of the acetal ester group as an acid-decomposable group during storage by steric hindrance and preventing deterioration of patterning properties, it is also preferable that Ra is a group represented by the following formula (IV) or (V).

In the above formula, Rc, Rd, Re, Rf and Rg each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, and Rc and Rd may be bonded to each other to form a ring, or at least two of Re, Rf and Rg may be bonded to each other to form a ring.
* indicates the binding site with other structures.
When Ra is a group represented by formula (IV) or formula (V), in a resin having a repeating unit represented by formula (1), the progress of an imidization reaction during storage can be suppressed, and a decrease in patterning properties can be prevented.
Examples of the alkyl group, cycloalkyl group, aryl group, or aralkyl group represented by Rc, Rd, Re, Rf, and Rg include the same alkyl group, cycloalkyl group, aryl group, and aralkyl group as those described above for _R36 .
The alkoxy group represented by Rc, Rd, Re, Rf and Rg is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms.
The alkyl group portion in the alkoxy group may be linear, branched or cyclic, or may be a combination of these.
The aryloxy group represented by Rc, Rd, Re, Rf and Rg is preferably an aryloxy group having 6 to 10 carbon atoms, and specific examples thereof include phenoxy, toluyloxy and 1-naphthoxy.
The alkoxycarbonyl group represented by Rc, Rd, Re, Rf, and Rg is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms, and specific examples thereof include methoxycarbonyl, ethoxycarbonyl, linear or branched propoxycarbonyl, cyclopentyloxycarbonyl, and cyclohexyloxycarbonyl.
The aryloxy moiety of the aryloxycarbonyl group represented by Rc, Rd, Re, Rf and Rg includes the same as the aryloxy group described above.

From the viewpoint of suppressing the decomposition of the acetal ester group as an acid-decomposable group during storage and preventing a decrease in patterning properties, it is preferable that at least one of Rc and Rd in formula (IV) is a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, and it is more preferable that at least one is an aryl group.

The divalent linking group represented by Rb is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 15 carbon atoms, such as a cyclopentylene group or a cyclohexylene group), -S-, -O-, -CO-, -CS-, -SO ₂ -, -N(R ₀ )-, or a combination of two or more of these, preferably having a total of 20 or less carbon atoms. Here, R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, an octyl group, or the like).
Rb is preferably a divalent linking group consisting of a single bond, an alkylene group, or a combination of an alkylene group and at least one of -O-, -CO-, -CS-, and -N(R ₀ )-, and more preferably a divalent linking group consisting of a single bond, an alkylene group, or a combination of an alkylene group and -O-, where R ₀ has the same meaning as R ₀ described above.

The alkyl group as Q is, for example, the same as the alkyl group as Ra described above.

Examples of the alicyclic group and aromatic ring group represented by Q include the cycloalkyl group and aryl group represented by Ra described above. The number of carbon atoms is preferably 3 to 18. In the present invention, the aromatic group represented by Q also includes a group in which a plurality of aromatic rings are linked via single bonds (e.g., a biphenyl group, a terphenyl group).
Examples of the alicyclic group containing a heteroatom and the aromatic ring group containing a heteroatom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, and pyrrolidone.
The alicyclic group and aromatic ring group represented by Q may have a substituent, and examples of such a substituent include an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, and an alkoxycarbonyl group.

Particularly preferred as (-Rb-Q) are a methyl group, an aryloxyethyl group, a cyclohexylethyl group or an arylethyl group, which improves solubility and thermal stability.

An example of a case in which at least two of Ra, Rb, and Q are bonded to each other to form a ring is when either Rb or Q is bonded to Ra to form a propylene group or a butylene group, thereby forming a five- or six-membered ring containing an oxygen atom.

If the sum of the carbon numbers of Ra, Rb and Q is expressed as N _C , when N _C is large, the change in the alkali dissolution rate of the resin before and after the group represented by formula (III) is eliminated becomes large, and the dissolution contrast becomes high contrast, improving the resolution. The range of N _C is preferably 2 to 20, and particularly preferably 2 to 15. When N _C is 20 or less, the glass transition temperature of the polymer compound is prevented from decreasing, and further, the generation of defects caused by the product eliminated from the acid-decomposable group adhering to the pattern is prevented.

At least one of Ra, Rb, and Q is preferably an electron-withdrawing group or a group having an electron-withdrawing group, which can suppress decomposition of the acid-decomposable group during storage in a resin having a repeating unit represented by formula (1), thereby preventing deterioration of patterning properties.
Examples of the electron-withdrawing group include an alkoxy group, an aryl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryloxy group, a nitrile group (cyano group), an alkylsulfonyl group, an arylsulfonyl group, and a nitro group. Of these, an alkoxy group, an aryl group, or an acyl group is preferable.

Specific examples of the group represented by formula (III) constituting the acetal ester group as an acid-decomposable group are shown below, but are not limited to these. * indicates the bonding site with other structures.

The thermal decomposition temperature of —CO ₂ R ³ in formula (1) is preferably 100 to 220° C., more preferably 120 to 210° C., and particularly preferably 140 to 200° C. The thermal decomposition temperature can be determined, for example, by differential thermogravimetry.
When the thermal decomposition temperature is equal to or higher than the lower limit, the storage stability of the resin composition of the present invention is improved, whereas when the thermal decomposition temperature is equal to or lower than the upper limit, the exposure sensitivity of the resin composition of the present invention is improved.

Specific examples of the structure of ^R3 that can achieve the above-mentioned thermal decomposition temperature include a structure in which at least one of _Rx1 to _Rx3 in the above formula (A1) is a group represented by the following formula (VI), and a structure in which Ra in the above formula (III) is a group represented by the above formula (IV) or the following formula (VII).

In the above formula (VI), R ₇ to R ₈ each independently represent a hydrogen atom, an alkyl group (linear or branched), or a cycloalkyl group (monocyclic or polycyclic), and at least one of R ₇ to R ₈ is a hydrogen atom. * represents a bonding site with another structure.

In the above formula (VII), Rh represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom. * represents a bonding site to another structure.
Specific and preferred examples of the alkyl group and cycloalkyl group for R ₇ to R ₈ include the same as the specific and preferred examples described above for the alkyl group and cycloalkyl group for Rx ₁ to Rx ₃ .
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group represented by Rh include the same as those described above for the alkyl group, cycloalkyl group, aryl group and aralkyl group for _R36 .
The alkoxy group represented by Rh is preferably an alkoxy group having 1 to 20 carbon atoms, and more preferably an alkoxy group having 1 to 6 carbon atoms.
The alkyl group portion in the alkoxy group may be linear, branched or cyclic, or may be a combination of these.
The aryloxy group represented by Rh is preferably an aryloxy group having 6 to 10 carbon atoms, and specific examples thereof include phenoxy, toluoyloxy, and 1-naphthoxy.
The alkoxycarbonyl group represented by Rh is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms, and specific examples thereof include methoxycarbonyl, ethoxycarbonyl, linear or branched propoxycarbonyl, cyclopentyloxycarbonyl, and cyclohexyloxycarbonyl.
The aryloxy moiety of the aryloxycarbonyl group represented by Rh includes the same as the aryloxy group described above.

Furthermore, ^R3 in formula (1) may be an organic group other than the group that is decomposed by the action of an acid to produce an alkali-soluble group.
Such an organic group can be used without particular limitation within the range in which the effects of the present invention can be obtained, and examples thereof include linear or branched alkyl groups, cycloalkyl groups, aryl groups, polyalkyleneoxy groups, etc. Preferred aspects of these groups are the same as the preferred aspects of these groups in R ₃₆ described above.

In the present invention, hydrogen atoms and organic groups can be mixed in R ^3. The ratio of organic groups to all R ^{3 in the resin is preferably 100 mol % to 20 mol %, and more preferably 100 mol % to 40 mol % of the organic groups. By adjusting the amount of hydrogen atoms and organic groups in R 3 ,} the dissolution rate in an alkaline aqueous solution changes, and by this adjustment, a resin composition having an appropriate dissolution rate can be obtained.
The proportion of groups that decompose under the action of an ^acid to generate an alkali-soluble group among all _{--CO.sub.2R.sub.3} in the resin, that is, the protection rate, is preferably 40 to 100%, and more preferably 45 to 100%.
In the present invention, a terminal blocking agent can be reacted with the terminal of the polymer mainly composed of the repeating unit represented by formula (1). As the terminal blocking agent, a monoalcohol, a phenol, a thiol, a thiophenol, a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, or the like can be used. By reacting with a terminal blocking agent, the number of repeating units, i.e., the molecular weight, can be controlled within a preferred range, which is preferable. Furthermore, the terminal blocking agent can suppress acid deactivation caused by neutralization of the terminal amine and the generated acid. In addition, by reacting a terminal blocking agent with the terminal, various organic groups, for example, crosslinking reactive groups having a carbon-carbon unsaturated bond, can be introduced as terminal groups.

Examples of monoalcohols used in the end-capping agent 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.

The monoamines used as end-capping agents are 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7- Aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene , 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid cyclic acid, 6-aminosalicylic acid, 3-amino-O-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene phthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2- Mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene , 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene Examples of the aminonaphthalene include, but are not limited to, 2-ethynyl-8-aminonaphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene, and aniline.

Of these, 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, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene Preferred are phthalene, 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, 4-aminothiophenol, 3-ethynylaniline, 4-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, and aniline.

Acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and active ester compounds used as end-capping agents include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, and 1-hydroxy-3-carboxynaphthalene. carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynyl dibenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, Monocarboxylic acids such as 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, and 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds in which the carboxy group of these acids is converted into an acid chloride, as well as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxypropyl ether, Examples of the monoacid chloride compound include monoacid chloride compounds in which only the monocarboxy groups of dicarboxylic acids such as diphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and 2,7-dicarboxynaphthalene are converted to acid chloride, and active ester compounds obtained by reacting the monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide.

Among these, acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, and 4-ethynylbenzoic acid are preferred. Preferred are monocarboxylic acids such as thynylbenzoic acid, 3,4-diethynylbenzoic acid, and 3,5-diethynylbenzoic acid, and monoacid chloride compounds in which the carboxy group of these is acid chlorided; monoacid chloride compounds in which only the monocarboxy group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene is acid chlorided; and active ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide.

The introduction ratio of the monoamine used in the terminal blocking agent is preferably in the range of 0.1 to 60 mol % relative to the total amine components, and particularly preferably 5 to 50 mol %. The introduction ratio of the compound selected from acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds used as terminal blocking agents is preferably in the range of 0.1 to 100 mol % relative to the diamine components, and particularly preferably 5 to 90 mol %. Multiple different terminal groups may be introduced by reacting multiple terminal blocking agents.

The end-capping agent introduced into the polymer can be easily detected by the following method. For example, the polymer into which the end-capping agent has been introduced is dissolved in an acidic solution and decomposed into amine components and acid anhydride components, which are the structural units of the polymer. The end-capping agent can be easily detected by measuring this by gas chromatography (GC) or NMR. In addition, the polymer component into which the end-capping agent has been introduced can also be easily detected by directly measuring the polymer component by pyrolysis gas chromatography (PGC), infrared spectrum, and ¹³ C NMR spectrum.

The specific resin used in the resin composition of the present invention is preferably one that is mainly composed of the repeating unit represented by formula (1). The term "main component" as used herein means that the repeating unit represented by formula (1) is contained in an amount of 70 mol% or more, more preferably 80 mol% or more, and most preferably 90 mol% or more.
The specific resin used in the present invention may be a copolymer of the repeating unit represented by formula (1) and another repeating unit, or may be a mixture of multiple resins containing the repeating unit represented by formula (1).
Furthermore, it may be a mixture of a resin containing a repeating unit represented by formula (1) and a resin not containing a repeating unit represented by formula (1) (for example, a resin in formula (1) that does not have a group that decomposes under the action of an acid to generate an alkali-soluble group in ^R3 ). In this case, the resin containing the repeating unit represented by formula (1) is preferably contained in an amount of 50 mass % or more, more preferably 75 mass % or more.
The type and amount of the repeating units used in copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polymer obtained by the final heat treatment.

From the viewpoints of alkali dissolution rate, film properties, etc., the resin containing the repeating unit represented by formula (1) preferably has a mass average molecular weight of 200,000 or less, more preferably from 1,000 to 200,000, even more preferably from 2,000 to 100,000, and particularly preferably from 3,000 to 100,000. By setting the molecular weight within this range, a photosensitive film having low stress, excellent mechanical properties, and excellent resolution with fewer development defects can be obtained.
The degree of dispersion (molecular weight distribution) is preferably from 1.0 to 7.0, and more preferably from 1.5 to 6.5.
In this specification, the degree of dispersion is a value calculated by weight average molecular weight/number average molecular weight.
In addition, when the resin composition contains a plurality of specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one of the specific resins 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 plurality of specific resins as one resin are each within the above ranges.

The specific resin of the present invention may be produced by any of the conventionally known methods (see, for example, Latest Polyimides - Basics and Applications (edited by the Japan Polyimide Research Association)).
For example, in the case of polyamic acid or polyamic acid ester, there are a method of reacting a tetracarboxylic dianhydride with a diamine compound at low temperature, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with an amine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with an amine, a method of imidizing a part of the carboxyl groups in the side chain by heat treatment or alkyl esterifying them using an esterification agent or the like, and the like.
Among these, a method (synthesis method 1) in which a diamine compound and a tetracarboxylic dianhydride are reacted in an organic solvent at −20 to 50° C. for several minutes to several days to obtain a polyamic acid, which is then reacted with a halide under basic conditions, with a vinyl ether under acidic conditions, or with a dialkyl acetal of dimethylformamide to obtain a resin containing a repeating unit represented by formula (1) is preferable in terms of cost, ease of operation, and performance reproducibility. Also, a method (synthesis method 2) in which a dicarboxylic acid having an acid-decomposable group as described in Makromol. Chem., 194, 511-521 (1993) is synthesized and then polycondensed with a diamine is preferable.
(Synthesis method 1)

(Synthesis method 2)

In the above scheme, R ¹ , R ² and R ³ have the same meanings as in formula (1).
Examples of organic solvents that can be used in the synthesis reaction of this polyamic acid include amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, and 1,3-dimethyl-2-imidazolidinone, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, and pyridine, halogen-based solvents such as chloroform, dichloromethane, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane, and ether-based solvents such as tetrahydrofuran, dioxane, and diglyme. Among these, amide-based solvents are preferred, and they are capable of producing a specific resin having a high molecular weight.

The boiling point of the organic solvent used in the polymerization reaction is preferably 50° C. or higher, more preferably 100° C. or higher, and particularly preferably 150° C. or higher.
The concentration of the solute in the reaction liquid is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 10 to 20% by mass.

A resin composition containing a specific resin is formed into a film on a substrate such as a semiconductor substrate, and if the resin composition is photosensitive (the formed film is a photosensitive film), a relief pattern can be formed by subsequent exposure and development steps. Heat treatment of this pattern causes dehydration and ring closure of the specific resin, resulting in a cured polyimide.

In the present invention, the specific resin has an i-line transmittance of 1% or more per 20 μm of film thickness, preferably 5% or more, more preferably 10% or more, and particularly preferably 10 to 80%. If this value is less than 1%, it is difficult to obtain a photosensitive resin composition capable of forming a high-resolution, well-shaped pattern. The i-line (light with a wavelength of 365 nm) transmittance can be measured using a spectrophotometer (e.g., Hitachi U3410 type, manufactured by Hitachi, Ltd.).

Furthermore, the residual stress of a cured polyimide formed by imide ring closure from a polyamic acid ester having a repeating unit represented by the above formula (1) is preferably 35 MPa or less, and more preferably 30 MPa or less.
The residual stress of the polyimide film can be measured at room temperature (25° C.) using a thin film stress measuring device (for example, FLX-2320 model, manufactured by Tencor Corporation).

A resin having a repeating unit represented by the above formula (1) that satisfies these properties has a structure in which the aromatic ring π-conjugation length is suppressed and a rigid and linear main chain can be formed, for example, by selecting an appropriate raw material during synthesis of the resin.
The content of the specific resin in the 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 resin composition. The content of the resin in the 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 resin composition.
In the present invention, the specific resin may be used alone or in combination.

<Other resins>
The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, 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 resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of or in addition to the polymerizable compound described later, by adding 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 content of polymerizable groups per 1 g of resin is 1×10 ⁻³ mol/g or more) to the resin composition, the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.

When the 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, based on the total solid content of the resin composition.
In addition, the content of other resins in the 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, still more preferably 60 mass% or less, and even more preferably 50 mass% or less, relative to the total solid content of the resin composition.
In addition, as a preferred embodiment of the 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 resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The 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.

[Photoacid generator]
The resin composition of the present invention 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 resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, onium salt compounds, and the like.
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 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 BisO CP-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, T riML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all product names, manufactured by Honshu Chemical Industries), BIR-OC, BI P-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product names, Examples of suitable phenols include, but are not limited to, 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.), and novolak resins.

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 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 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. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom, or an alkyl group is preferable, and an embodiment in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group is also preferable. Among them, an embodiment in which R ^u1 to R ^u4 are all hydrogen atoms is preferable. Any of the above-mentioned substituents may further have a substituent.

市販品としては、ＷＰＡＧ－３３６（富士フイルム和光純薬（株）製）、ＷＰＡＧ－４４３（富士フイルム和光純薬（株）製）、ＭＢＺ－１０１（みどり化学（株）製）等を挙げることができる。 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-2001-132318, 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.

式（ＲＩ－Ｉ）中、Ａｒ_１１は置換基を１～６有していても良い炭素数２０以下のアリール基を表し、好ましい置換基としては炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数６～１２のアリール基、炭素数１～１２のアルコキシ基、炭素数１～１２のアリーロキシ基、ハロゲン原子、炭素数１～１２のアルキルアミノ基、炭素数２～１２のジアルキルアミノ基、アルキル基の炭素数が１～１２のアルキルアミド基又はアリール基の炭素数が６～２０のアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数１～１２のチオアルキル基、炭素数１～１２のチオアリール基が挙げられる。Ｚ_１１ ^－は１価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオンが好ましい。式（ＲＩ－ＩＩ）中、Ａｒ_２１、Ａｒ_２２は各々独立に置換基を１～６有していてもよい炭素数１～２０のアリール基を表し、好ましい置換基としては炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数１～１２のアリール基、炭素数１～１２のアルコキシ基、炭素数１～１２のアリーロキシ基、ハロゲン原子、炭素数１～１２のモノアルキルアミノ基、アルキル基の炭素数がそれぞれ独立に１～１２のジアルキルアミノ基、アルキル基の炭素数が炭素数１～１２のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数１～１２のチオアルキル基、炭素数１～１２のチオアリール基が挙げられる。Ｚ２１^－は１価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。式（ＲＩ－ＩＩＩ）中、Ｒ_３１、Ｒ_３２、Ｒ_３３は各々独立に置換基を１～６有していても良い炭素数６～２０のアリール基又はアルキル基、アルケニル基、アルキニル基を表し、好ましくは反応性、安定性の面から、アリール基であることが望ましい。好ましい置換基としては炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数１～１２のアリール基、炭素数１～１２のアルコキシ基、炭素数１～１２のアリーロキシ基、ハロゲン原子、炭素数１～１２のモノアルキルアミノ基、アルキル基の炭素数がそれぞれ独立に炭素数１～１２のジアルキルアミノ基、アルキル基の炭素数が炭素数１～１２のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシ基、シアノ基、スルホニル基、炭素数１～１２のチオアルキル基、炭素数１～１２のチオアリール基が挙げられる。Ｚ_３１ ^－は１価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。 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 used in an amount of preferably 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 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 in order to impart photosensitivity to a desired light source.

<Solvent>
The resin composition of the present invention 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 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 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.

<Acid Scavenger>
The 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.

<Heat curing accelerator>
The resin composition may contain a heat curing accelerator.
Examples of the thermal curing accelerator include a thermal polymerization initiator and a thermal acid generator.
In the case where the resin composition contains a radical crosslinking agent as a polymerizable compound, a thermal polymerization initiator may be included, and in the case where the resin composition contains another crosslinking agent, a thermal acid generator may be included.

[Thermal Polymerization Initiator]
The thermal polymerization initiator may particularly include a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, 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 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.

[Thermal acid generator]
The resin composition may contain a thermal acid generator.
The thermal acid generator generates an acid upon heating, and has the effect of promoting the crosslinking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound.

The thermal decomposition starting temperature of the thermal acid generator is preferably 50° C. to 270° C., more preferably 50° C. to 250° C. In addition, it is preferable to select as the thermal acid generator a material that does not generate acid during drying (pre-baking: about 70 to 140° C.) after the composition is applied to a substrate, but generates acid during final heating (cure: about 100 to 400° C.) after patterning by subsequent exposure and development, because this can suppress a decrease in sensitivity during development.
The thermal decomposition initiation temperature is determined as the lowest exothermic peak temperature when the thermal acid generator is heated to 500° C. at 5° C./min in a pressure-resistant capsule.
An example of an instrument used to measure the thermal decomposition onset temperature is Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid, or a haloalkylsulfonic acid such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of JP 2013-072935 A.

Among these, from the viewpoint of having little residue in the cured product (cured film) and being less likely to deteriorate the physical properties of the cured product (cured film), those that generate alkylsulfonic acids having 1 to 4 carbon atoms or haloalkylsulfonic acids having 1 to 4 carbon atoms are more preferred, and examples thereof include (4-hydroxyphenyl)dimethylsulfonium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl (4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium methanesulfonate, (4-hydroxyphenyl)methyl ((2-methylphenyl)methyl)sulfonium methanesulfonate, and (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate. Methylsulfonium, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propanenitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred as the thermal acid generator.

In addition, the compounds described in paragraph 0059 of JP-A-2013-167742 are also preferred as thermal acid generators.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, per 100 parts by mass of the resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the cured product (cured film) can be further improved. In addition, from the viewpoint of the electrical insulation of the cured product (cured film), 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is even more preferable.

<Base Generator>
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Examples of base generators that are preferable for the resin composition of the present invention include a thermal base generator and a photobase generator.
In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package can be improved.
The base generator may be an ionic base generator or a nonionic 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 more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and is preferably 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 more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably 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.

（Ｂ３）

(B3)

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 of such groups include methyloxymethylmethyl (MOM) and ethyloxyethyl (EE). 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 (e.g., 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 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 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.

<Polymerizable Compound>
The resin composition of the present invention preferably contains a polymerizable compound.
The polymerizable compound may include a radical crosslinking agent or other crosslinking agents.

[Radical Crosslinking Agent]
The 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 the like.
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 pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the 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, difunctional 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 Examples of the oligomer include 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 a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound, 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 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, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as necessary.
For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain.
In the resin composition of the present invention, from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern (cured product), 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 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 resin composition of the present invention also 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 is preferably an acid generated from a photoacid 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 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 of the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 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 ester 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, or tetrabutoxymethylated glycoluril; bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea urea-based crosslinking agents such as monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea; ethylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea; Examples of the crosslinking agent include propylene urea-based crosslinking agents such as dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, and dibutoxymethylated propylene urea; 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

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 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 curing the resin composition of the present invention at low temperatures and suppressing warping.

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-3000 -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 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.

<Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in 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 the specific resin. By making the content equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the above 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 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 originating 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 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 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 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, 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-nitrosophenylhydroxyamine 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-sulfopropylamino)phenol, 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 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbonate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like are preferably used. In addition, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 A can also be used, the contents of which are incorporated herein by reference.

When the 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 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.

<Other additives>
The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, 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 range 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 found, for example, in the descriptions in paragraphs 0183 and after 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 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 photosensitive 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 3,000 to 50,000, and more preferably 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 as the fluorosurfactant. 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. In addition, examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., 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, Inc.), KP341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone 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 KP341 (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, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during drying after application.

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 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 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.

[Inorganic particles]
The resin composition of the present invention may contain inorganic fine particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

The average particle size of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, even more preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm.
The above average particle size of the fine particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
When the above measurements are difficult, the measurements can also be made by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method.

[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 resin composition of the present embodiment may contain an organotitanium compound. By containing an organotitanium compound in the 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 they provide a resin composition with good storage stability and a good curing pattern. 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 the specific resin. 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 high temperature and high humidity environments, and by adding an amount of 10 parts by mass or less, the sensitivity of the 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 is within the above range.

[Anti-aggregation agent]
The 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 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 from 0.01% by mass to 30% by mass, and more preferably from 0.02% by mass to 20% by mass, relative to the total solid 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 Resin Composition>
The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the 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 3,000 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 less, it is difficult to apply it with a film thickness required for, for example, a rewiring insulating film, and if it is 12,000 mm ² /s or more, the coating surface condition may deteriorate.

<Restrictions on substances contained in resin composition>
The water content of the 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 water content is 2.0% or more, the storage stability of the resin composition may be impaired.
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 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, methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the 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 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.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 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 prevent impurities from being mixed into the raw materials or the resin composition of the present invention. Examples of such containers include the container described in JP 2015-123351 A.

<Cured Product of Resin Composition>
By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
The resin composition is preferably cured by heating, and the heating temperature is preferably within the range of 120°C to 400°C, more preferably within the range of 140°C to 380°C, and particularly preferably within the range of 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as film-like, rod-like, spherical, pellet-like, etc. In the present invention, the cured product is preferably in the form of a film. In addition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function, by pattern processing of the resin composition. The film thickness of this cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage percentage refers to the percentage of the volume change before and after curing of the resin composition, and can be calculated by the following formula.
Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) x 100

<Characteristics of the cured product of the resin composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is less than 70%, the mechanical properties of the cured product may be poor.
The breaking elongation of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

(Developer)
The developer of the present invention is a developer used in the method for producing a cured product of the present invention.
The developer of the present invention has the same meaning as the developer explained in the developing step of the method for producing a cured product of the present invention, and preferred embodiments are also the same.

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.

一口フラスコに、２－フェニルプロピオンアルデヒド（東京化成工業（株）製）３４．９０ｇ（２６０ミリモル）、エチレングリコールモノプロピルエーテル（東京化成工業（株）製）５９．６０ｇ（５７２ミリモル）、（±）－１０－カンファースルホン酸（東京化成工業（株）製）０．６ｇ（２．６ミリモル）、硫酸マグネシウム（東京化成工業（株）製）３０ｇを加えて反応溶液を得た。得られた反応溶液を２５℃で３０分撹拌した後５０℃に昇温し、２４時間撹拌した。攪拌後の溶液を２５℃に冷却し、トリエチルアミン（東京化成工業（株）製）１．３２ｇ（１３ミリモル）を添加した後、酢酸エチル５００ｍＬに溶解し、分液ロートに移した。分液ロート中の酢酸エチル溶液を飽和重曹水２００ｍＬで３回洗浄した後、エバポレーターで溶媒を除去し、アセタール体Ａ－１を７２ｇ得た。 <Synthesis of acetals A-1 and A-2>

Into a one-neck flask, 34.90 g (260 mmol) of 2-phenylpropionaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 59.60 g (572 mmol) of ethylene glycol monopropyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.6 g (2.6 mmol) of (±)-10-camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 30 g of magnesium sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to obtain a reaction solution. The obtained reaction solution was stirred at 25°C for 30 minutes, then heated to 50°C and stirred for 24 hours. The solution after stirring was cooled to 25°C, and 1.32 g (13 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and then dissolved in 500 mL of ethyl acetate and transferred to a separatory funnel. The ethyl acetate solution in the separatory funnel was washed three times with 200 mL of saturated sodium bicarbonate water, and the solvent was removed with an evaporator to obtain 72 g of acetal body A-1.

Acetal A-2 was synthesized in a similar manner.

<Synthesis of chlorinated bodies B-1 and B-2>
A reaction solution was obtained by adding 72 g of the A-1 synthesized above and 19.1 g (243 mmol) of acetyl chloride (Tokyo Chemical Industry Co., Ltd.) to a one-neck flask. The reaction solution obtained was stirred at 25° C. for 1 hour, then heated to 45° C. and stirred for 4 hours to obtain 91 g of chlorinated body B-1.

Chlorinated compound B-2 was synthesized in a similar manner.

<Synthesis Example: Synthesis of Polymer P-1>
31.02 g (100 mmol) of 4,4'-oxydiphthalic dianhydride and 145 g of N-methylpyrrolidone (NMP) were added to a flask, and then 18.02 g (90 mmol) of 4,4'-diaminodiphenyl ether was added with stirring at 25° C. After stirring for 3 hours, 130 g of NMP was added for dilution.
The obtained diluted solution was cooled to -5°C or lower, and then 25.85 g (200 mmol) of diisopropylethylamine was added dropwise over 30 minutes, and then 24.91 g (200 mmol) of 2-methoxyethoxymethyl chloride (Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour, and the mixture was stirred at -10 to -5°C for 1 hour. The obtained solution after stirring was added to 5 L of methanol and stirred for 30 minutes. The solution after stirring was allowed to stand for 30 minutes, and the supernatant liquid was discarded to obtain a solid. This solid was dissolved in 300 mL of tetrahydrofuran, added to 5 L of hexane, stirred for 30 minutes, and then filtered and dried to obtain 56 g of polymer P-1.

<Synthesis Example: Synthesis of Polymer P-2>
A flask was charged with 9.64 g (130 mmol) of t-butyl alcohol and 30 mL of tetrahydrofuran, and the mixture was cooled to −10° C., after which 43.7 g of n-butyllithium (20% by mass solution in cyclohexane) was added dropwise to obtain TB-1.
In a flask different from the above, 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride was suspended in 100 mL of diglyme, and 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were added successively. The entire amount of TB-1 was then added dropwise over 1 hour using a dropping funnel, and the mixture was then stirred at a temperature of 25°C for 5 hours. The resulting mixture was cooled to -10°C, and 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes to obtain a white precipitate of pyridinium hydrochloride. The mixture containing the white precipitate was then warmed to room temperature and stirred for 2 hours, after which 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a solution. Next, a solution obtained by dissolving 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of NMP was added dropwise to the obtained solution over 1 hour. 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added to the obtained mixture, and then the mixture was stirred for 2 hours. Next, the mixture after stirring was added to 4 liters of water to precipitate a polyimide precursor resin, and then the mixture was stirred at a speed of 500 rpm for 15 minutes. After the polyimide precursor resin was obtained by filtration, the obtained polyimide precursor resin was added to 4 liters of water, stirred again for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45°C for 3 days to obtain 33 g of P-2.

<Synthesis Example: Synthesis of Polymer P-3>
Polymer P-3 was synthesized in the same manner as P-1, except that an equimolar amount of B-1 was used instead of 2-methoxyethoxymethyl chloride.

<Synthesis Example: Synthesis of Polymer P-4>
Polymer P-4 was synthesized in the same manner as P-1, except that an equimolar amount of B-2 was used instead of 2-methoxyethoxymethyl chloride.

<Synthesis Example: Synthesis of Polymer P-5>
29.42 g (100 mmol) of 4,4'-biphthalic anhydride and 145 g of N-methylpyrrolidone (NMP) were added to a flask, and then 18.02 g (90 mmol) of 4,4'-diaminodiphenyl ether was added with stirring at 25° C. After stirring for 3 hours, 130 g of NMP was added for dilution.
The obtained diluted solution was cooled to -5°C or lower, and then 25.85 g (200 mmol) of diisopropylethylamine was added dropwise over 30 minutes, and then 72.4 g (200 mmol) of B-2 (the above synthesized product) was added dropwise over 1 hour, and the mixture was stirred at -10 to -5°C for 1 hour. The obtained solution after stirring was added to 5 L of methanol and stirred for 30 minutes. The solution after stirring was allowed to stand for 30 minutes, and the supernatant was discarded to obtain a solid. This solid was dissolved in 300 mL of tetrahydrofuran, added to 5 L of hexane, and stirred for 30 minutes, followed by filtration and drying to obtain 52 g of polymer P-5.

<Synthesis Example: Synthesis of Polymer P-6>
Polymer P-6 was synthesized in the same manner as P-1, except that the amount of 4,4'-diaminodiphenyl ether added was changed to 16.0 g (80 mmol).

<Examples and Comparative Examples>
In each of the examples, the components shown in the following table were mixed to obtain a resin composition. In each of the comparative examples, the components shown in the following table were mixed to obtain a comparative composition.
Specifically, the content of each component in the table was the amount shown in the "Parts by mass" column in the table. The content of the solvent in each composition was adjusted so that the solids concentration of the composition was the value (% by mass) shown in the table.
The obtained resin composition and comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a filter pore size of 0.8 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-6: P-1 to P-6 synthesized above

[Crosslinking agent (polymerizable compound)]
B-1 to B-4: Compounds having the following structure

[Photoacid generator]
C-1 to C-4: Compounds having the following structure

[Photopolymerization initiator]
I-1: Irgacure OXE-01 (manufactured by BASF)

[Silane coupling agent]
D-1: 3-glycidoxypropylmethyldimethoxysilane D-2: Compound having the following structure

[Migration Inhibitor]
E-1: Tetrazole

[Additive (acid scavenger)]
F-1: Tridodecylamine F-2: Triphenylimidazole F-3: DBU (diazabicycloundecene)

〔solvent〕
GBL: γ-butyrolactone DMSO: dimethylsulfoxide In the table, the entries in the "Ratio" column indicate the content (mass %) of each solvent relative to the total mass of the solvents.

(evaluation)
<Resolution evaluation>
In each of the examples and comparative examples, the resin composition or the comparative composition was applied onto a silicon substrate by spin coating to form a coating film. Then, a hot plate was used to perform a heat treatment for 300 seconds at the temperature shown in the "PB temperature (°C)" column in the table to form a resin composition layer. The thickness of the resin composition layer was appropriately changed so that the film thickness after rinsing was the value shown in the "film thickness after modification (μm)" column in the table.
Next, the resin composition layer was exposed to light using an i-line filter with a broadband exposure machine (UX-1000SN-EH01 manufactured by Ushio Inc.). The exposure dose was 400 mJ/cm ^2. As a photomask, a Toppan Test Chart (No. 1, negative type, manufactured by Toppan Printing Co., Ltd.) was used.
After exposure, the resin composition layer was heated for 300 minutes using a hot plate at the temperature shown in the "PEB temperature (°C)" column in the table. In the examples with "-" in the "PEB temperature (°C)" column, heating was not performed.
After the above heating, development was carried out at 23° C. for 60 seconds using the developer shown in the “Developer” column in the table to form a pattern.
After the above development, the substrate was rinsed with PGMEA (propylene glycol monomethyl ether acetate).
After development, the resulting patterns were observed and evaluated according to the following evaluation criteria. The evaluation results are shown in the "Resolution" column in the table.
-Evaluation criteria-
A: The minimum opening diameter was 10 μm or less.
B: The minimum opening diameter was more than 10 μm and 20 μm or less.
C: The minimum opening diameter exceeded 20 μm.

<Evaluation of dimensional stability of the first layer when stacking multiple layers>
[Formation of the first layer]
In each of the examples and comparative examples, the resin composition or the comparative composition was applied to a silicon substrate by spin coating to form a coating film. Then, a hot plate was used to perform a heat treatment for 300 seconds at the temperature shown in the "PB temperature (°C)" column in the table to form a resin composition layer. The thickness of the resin composition layer was appropriately changed so that the film thickness after modification was the value shown in the "film thickness after modification (μm)" column in the table.
Next, the resin composition layer was exposed to light using a stepper exposure device FPA-3000i5+ (manufactured by Canon Corporation) using a photomask on which a 1:1 line and space pattern with a line width of 20 μm was formed. The exposure dose was 400 mJ/ ^cm2 .
After exposure, the resin composition layer was heated for 5 minutes using a hot plate at the temperature shown in the "PEB temperature (°C)" column in the table. In the examples with "-" in the "PEB temperature (°C)" column, heating was not performed.
After the above heating, development was carried out at 23° C. for 60 seconds using the developer shown in the “Developer” column in the table to form a pattern.
After the above development, the substrate was rinsed with PGMEA (propylene glycol monomethyl ether acetate).
The above pattern was heated at the temperature shown in "Cure temperature (° C.)" and for the time shown in "Cure time (min)" in the table to obtain a first layer pattern.
In the examples where " _N2 oven" is listed in the "Heating means" column, heating was performed using CLH-21 manufactured by Koyo.
In the examples where "IR oven" is listed in the "Heating means" column, heating was performed using an RTP-6 manufactured by Advance Riko.

[Formation of the second layer]
In each of the examples and comparative examples, the same resin composition or comparative composition was applied again on the cured product of the first layer by spin coating to form a coating film. Then, a hot plate was used to perform a heat treatment for 300 seconds at the temperature listed in the "PB temperature (°C)" in the table to form a resin composition layer. The thickness of the resin composition layer was appropriately changed so that the film thickness after modification was the value listed in the "film thickness after modification (μm)" column in the table.
Next, the resin composition layer was exposed to light using a stepper exposure device FPA-3000i5+ (manufactured by Canon Corporation) using a photomask on which a 1:1 line and space pattern with a line width of 20 μm was formed. The exposed portion through the 1:1 line and space pattern was set so that the line portion and the space portion were orthogonal to the exposed portion in the first layer. The exposure dose was 400 mJ/ ^cm2 .
After exposure, the resin composition layer was heated for 5 minutes using a hot plate at the temperature shown in the "PEB temperature (°C)" column in the table. In addition, in the examples shown with "-" in the "PEB temperature (°C)" column, heating was not performed.
After the above heating, development was carried out at 23° C. for 60 seconds using the developer shown in the “Developer” column in the table to form a pattern.
After the above development, the substrate was rinsed with PGMEA (propylene glycol monomethyl ether acetate).
The above pattern was heated at the temperature shown in "Cure temperature (° C.)" for the time shown in "Cure time (min)" in the table.
In the examples where " _N2 oven" is written in the "Heating means" column, heating was performed using CLH-21 manufactured by Koyo to obtain a cured product for the second layer.
In the examples where "IR oven" is listed in the "Heating means" column, heating was performed using an RTP-6 manufactured by Advance Riko Co., Ltd. to obtain a cured product for the second layer.

〔evaluation〕
The line width (line width A) of the cured product of the first layer immediately after the formation of the cured product of the first layer (before the formation of the coating film in the formation of the second layer) and the line width (line width B) of the cured product of the first layer immediately after the formation of the cured product of the second layer were measured, and the dimensional variation (%) was calculated according to the following formula. From the dimensional variation value, the dimensional stability of the first layer was evaluated according to the following evaluation criteria. The evaluation results are shown in the column "Evaluation of dimensional stability of first layer when laminated in multiple layers".
Dimensional variation (%) = |Line width A - Line width B| / Line width A x 100 - Evaluation standard -
A: The dimensional variation (%) was 5% or less.
B: The dimensional variation (%) exceeded 5%.

<Evaluation of the resolution of the second layer when multiple layers are laminated>
A cured product of the first layer and a cured product of the second layer were prepared in the same manner as in the evaluation of the dimensional stability of the first layer during multi-layer lamination.
The cured product of the second layer was observed and evaluated according to the following evaluation criteria. The evaluation results are shown in the column "Evaluation of resolution of second layer when multi-layered" in the table.
-Evaluation criteria-
A: The taper angle between the substrate surface and the side surface of the pattern was 80° or more and less than 90°, and peeling of the pattern was not observed.
B: The taper angle was less than 80°, or the cross-sectional shape of the pattern was an inverse taper shape with a taper angle exceeding 90°, or the cross-sectional shape of the pattern was a constricted shape, but peeling of the pattern was not observed.
C: Peeling of the pattern was observed.

In the method for producing a cured product according to Comparative Example 1, the polyimide precursor does not have a group that undergoes a reaction that increases polarity under the action of an acid, and so-called negative pattern formation is performed. In such an example, it is clear that the resolution is poor.

<Example 101>
The resin composition used in Example 1 was applied in a layer form by spin coating on the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed, and dried at 100°C for 300 seconds. The film thickness was set so that the film thickness of the resulting cured product would be 5 μm. Thereafter, exposure was performed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line and space pattern and a line width of 10 μm). After exposure, heating was performed at 120°C for 300 seconds. After the above heating, development was performed with the developer used in Example 1, and rinsing was performed with the rinse solution used in Example 1 to obtain a layer pattern.
Next, the temperature was increased at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained for 120 minutes to harden the layer, forming an interlayer insulating film for a rewiring layer. 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 (11)

a film-forming step of applying a resin composition containing a resin, a compound that generates an acid upon irradiation with actinic rays or radiation, an acid scavenger, and a solvent onto a substrate to form a film;
an exposure step of selectively exposing the film;
A developing step of developing the exposed film with a developer to form a pattern; and
A modification step of modifying the pattern,
the resin is a polyimide precursor,
The resin has a group that undergoes a reaction to increase polarity by the action of an acid,
The content of the organic solvent in the developer is 80% by mass or more based on the total mass of the developer,
In the modification step, the pattern is heated at a heating temperature of 160 to 230° C., and the modification reduces the solubility of the pattern in a solvent contained in the resin composition.
A method for producing a cured product. The method for producing a cured product according to claim 1, wherein the film thickness of the resulting cured product is 5 μm or more. The method for producing a cured product according to claim 1 or 2, wherein the resin contains a repeating unit represented by the following formula (1):

In the above formula (1), R ¹ represents a tetravalent organic group; multiple R ^1s may be the same or different; R ² represents a divalent organic group; multiple R ^2s may be the same or different; and each R ³ independently represents a hydrogen atom or an organic group. The method for producing a cured product according to claim 3, wherein the repeating unit represented by formula (1) has a group that undergoes a reaction that increases polarity under the action of the acid. The method for producing a cured product according to any one of claims 1 to 4, wherein the developer contains 80% by mass or more of an organic solvent having a value of the hydrogen bond term dH of the Hansen solubility parameters of 8 or less. The method for producing a cured product according to any one of claims 1 to 5, wherein the group that undergoes a reaction to increase polarity by the action of an acid is a group represented by the following formula (A-1) or the following formula (A-2):
In formula (A-1), R ^A1 to R ^A5 each independently represent a hydrogen atom or a monovalent organic group, at least two of R ^A1 to R ^A5 may be bonded to form a ring structure, and * represents a bonding site to another structure;
In formula (A-2), R ^A6 to R ^A8 each independently represent a monovalent organic group, at least two of R ^A6 to R ^A8 may be bonded to form a ring structure, and * represents a bonding site to another structure. The method for producing a cured product according to any one of claims 1 to 6 further comprises a step of heating the film after the exposure step and before the development step. A method for producing a laminate, comprising repeating the method for producing a cured product according to any one of claims 1 to 7 multiple times. The method for producing a laminate according to claim 8 further includes a metal layer forming step of forming a metal layer on a layer of the cured product between the multiple processes for producing the cured product. A method for producing a cured product according to any one of claims 1 to 7, or a method for producing a laminate according to claim 8 or 9,
A method for manufacturing an electronic device. A resin composition used in the method for producing a cured product according to any one of claims 1 to 7.