JP6633767B2 - Method for manufacturing laminate and method for manufacturing electronic device - Google Patents

Description

  The present invention relates to a method for manufacturing a laminate and a method for manufacturing an electronic device.

  BACKGROUND ART Resins such as polyimide and polybenzoxazole have excellent heat resistance and insulating properties, and are therefore used for insulating layers of electronic devices. In addition, since polyimide and polybenzoxazole have low solubility in a solvent, they are applied to a support or the like in the state of a precursor (polyimide precursor or polybenzoxazole precursor) before the cyclization reaction, and then heated. Cyclization of a polyimide precursor or a polybenzoxazole precursor to form a cured film has also been performed.

  For example, Patent Documents 1 and 2 describe manufacturing a pattern cured film using a photosensitive resin composition containing a polyimide precursor and a photopolymerization initiator.

JP 2011-191749 A JP 2014-201695 A

  The present inventors have studied a photosensitive resin composition containing a polyimide precursor, a polyimide, a resin selected from a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator. It has been found that a film formed using a photosensitive resin composition containing the same may have insufficient adhesion to a support or a metal layer.

  Accordingly, it is an object of the present invention to provide a method for manufacturing a laminate having excellent adhesion and a method for manufacturing an electronic device.

Under the above-mentioned problems, as a result of study by the inventors, a polyimide resin, a polyimide, a resin selected from a polybenzoxazole precursor and a polybenzoxazole, and a photosensitive resin composition containing a photopolymerization initiator, It has been found that the film formed by using the method tends to require time until the properties of the film are stabilized after being applied on a support. Then, it has been found that by providing a predetermined storage step in any of the steps described below, a laminate having excellent adhesion can be manufactured, and the above problem has been solved. The present invention provides the following.
<1> A photosensitive resin composition containing a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator is applied on a support to form a photosensitive resin composition. Photosensitive resin composition layer forming step of forming a material layer,
An exposure step of exposing the photosensitive resin composition layer to a pattern,
A developing step of developing the photosensitive resin composition layer to form a pattern,
A heating step of heating the pattern,
Metal layer forming step of forming a metal layer on the pattern after heating,
Between the photosensitive resin composition layer forming step and the exposing step, between the exposing step and the developing step, between the developing step and the heating step, and at least one between the heating step and the metal layer forming step A method for producing a laminate, comprising performing a preservation step of preserving the surface temperature for 5 minutes or more after the surface temperature reaches a certain temperature.
<2> The method for producing a laminate according to <1>, wherein a storage step is performed between the exposure step and the development step.
<3> The method for producing a laminate according to <2>, wherein the storage step performed between the exposure step and the development step satisfies the following formula;
5 ≦ t1 <( ^{10−0.036 × T1 + 12.3} ) × 60
T1 is the average surface temperature in the storage step performed between the exposure step and the development step, and is expressed in K; t1 is the time of the storage step performed between the exposure step and the development step, in minutes. is there.
<4> The method for producing a laminate according to any one of <1> to <3>, wherein a storage step is performed between the photosensitive resin composition layer forming step and the exposure step.
<5> The method for producing a laminate according to <4>, wherein the storage step performed between the photosensitive resin composition layer forming step and the exposure step satisfies the following formula;
5 ≦ t2 <( ^{10−0.031 × T2 + 10.7} ) × 60
T2 is the average surface temperature in the storage step performed between the photosensitive resin composition layer forming step and the exposing step, and the unit is K; t2 is between the photosensitive resin composition layer forming step and the exposing step. The time of the preservation step to be performed, the unit being minutes.
<6> The method for producing a laminate according to any one of <1> to <5>, wherein a storage step is performed between the developing step and the heating step.
<7> The method for producing a laminate according to <6>, wherein the storage step performed between the development step and the heating step satisfies the following equation;
5 ≦ t3 <( ^{10−0.02 × T3 + 8.0} ) × 60
T3 is the average surface temperature in the storage step performed between the development step and the heating step, and is expressed in K; t3 is the time of the storage step performed between the development step and the heating step, in minutes. is there.
<8> The method for producing a laminate according to any one of <1> to <7>, wherein a storage step is performed between the heating step and the metal layer forming step.
<9> The resin in the photosensitive resin composition is a polyimide precursor, and the polyimide precursor contains a radical polymerizable group, or the photosensitive resin composition contains a radical polymerizable compound other than the polyimide precursor. 1> The method for producing a laminate according to any one of <8>.
<10> The method for producing a laminate according to any one of <1> to <9>, wherein the polyimide precursor includes a repeating unit represented by the following formula (1);
Equation (1)
In the formula (1), A ²¹ and A ²² each independently represent an oxygen atom or —NH—, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group.
<11> The method for producing a laminate according to <10>, wherein in formula (1), at least one of R ²³ and R ²⁴ includes a radically polymerizable group.
<12> The method for producing a laminate according to <10> or <11>, wherein R ²² in the formula (1) is a tetravalent group containing an aromatic ring.
<13> On the pattern after the metal layer forming step, a photosensitive resin composition layer forming step, an exposure step, a developing step, a heating step and a metal layer forming step are performed in this order, and Between the exposure step, between the exposure step and the development step, between the development step and the heating step, and at least one between the heating step and the metal layer forming step, a series of cycles to perform a storage step The method for producing a laminate according to any one of <1> to <12>, wherein the method comprises performing two or more cycles.
<14> The method for producing a laminate according to any one of <1> to <13>, which is a method for producing a laminate having a multilayer wiring structure.
<15> A photosensitive resin composition containing a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator is applied on a support to form a photosensitive resin composition. Photosensitive resin composition layer forming step of forming a material layer,
An exposure step of exposing the photosensitive resin composition layer to a pattern,
A developing step of developing the photosensitive resin composition layer to form a pattern,
A heating step of heating the pattern,
Metal layer forming step of forming a metal layer on the pattern after heating,
Between the photosensitive resin composition layer forming step and the exposing step, between the exposing step and the developing step, between the developing step and the heating step, and at least one between the heating step and the metal layer forming step And a method for manufacturing an electronic device, including a method for manufacturing a laminate, in which a storage step is performed in which the surface temperature reaches a certain temperature and stored for 5 minutes or more in that state.
<16> The method for manufacturing an electronic device according to <15>, wherein a plurality of electronic devices are manufactured under the same storage process conditions.

  ADVANTAGE OF THE INVENTION By this invention, it became possible to provide the manufacturing method of the laminated body excellent in adhesiveness, and the manufacturing method of an electronic device.

It is the schematic which shows the structure of one Embodiment of a laminated body. FIG. 1 is a schematic diagram illustrating a configuration of an embodiment of an electronic device.

The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of a group (atomic group) in the present specification, the notation of not indicating substituted or unsubstituted includes a group having a substituent as well as a group having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “exposure” includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam, unless otherwise specified. The light used for exposure generally includes an active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet represented by excimer laser, extreme ultraviolet (EUV light), X-ray, and electron beam.
In this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the present specification, “(meth) acrylate” represents both or “acrylate” and “methacrylate”, and “(meth) allyl” represents both “allyl” and “methallyl”, or Represents either, “(meth) acryl” represents both “acryl” and “methacryl” or either, and “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Indicates one of them.
In the present specification, the term "step" is included not only in an independent step but also in the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. .
In the present specification, the solid content concentration is a mass percentage of the other components excluding the solvent with respect to the total mass of the composition. The solid content concentration means a concentration at 25 ° C. unless otherwise specified.
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC) measurement, unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined, for example, using HLC-8220 (manufactured by Tosoh Corporation) and using a guard column HZ-L, TSKgel Super HZM-M, TSKgel as a column. It can be determined by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). The eluent is THF (tetrahydrofuran) unless otherwise specified. Unless otherwise specified, detection is performed using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).

<Production method of laminate>
The method for producing a laminate of the present invention comprises, on a support, a photosensitive resin composition containing a polyimide precursor, a polyimide, a resin selected from a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator. A photosensitive resin composition layer forming step of applying to form a photosensitive resin composition layer,
An exposure step of exposing the photosensitive resin composition layer to a pattern,
A developing step of developing the photosensitive resin composition layer to form a pattern,
A heating step of heating the pattern,
Metal layer forming step of forming a metal layer on the pattern after heating,
Between the photosensitive resin composition layer forming step and the exposing step, between the exposing step and the developing step, between the developing step and the heating step, and at least one between the heating step and the metal layer forming step After the surface temperature reaches a certain temperature, a preservation step of preserving the state for 5 minutes or more is performed.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in adhesiveness can be formed. It is presumed that the reason for obtaining such an effect is as follows. A film formed using a photosensitive resin composition containing the above-described resin and a photopolymerization initiator tends to require time until the properties of the film are stabilized. When the next process (for example, after performing the photosensitive resin composition layer forming process and then performing the exposure process) is performed in a state where the properties of the film are not stable, a portion where a reaction locally progresses in the film or the like It is considered that the stress is locally applied to the film due to the occurrence of the stress. On the other hand, according to the present invention, by providing the above-mentioned storage step between any of the above-mentioned steps, the properties of the film are stabilized, and the residual stress of the film is alleviated. It is believed that the process can be performed. For this reason, it is presumed that a laminate having excellent adhesion could be produced.
Further, the above-described resin in the photosensitive resin composition is a polyimide precursor, and the polyimide precursor contains a radical polymerizable group, or a photosensitive resin composition containing a radical polymerizable compound other than the above-described polyimide precursor. When a product is used, the effect of the present invention is particularly remarkable. Although the detailed reason is unknown, when a photosensitive resin containing such a radical polymerizable component (a polyimide precursor having a radical polymerizable group, a radical polymerizable compound other than the polyimide precursor) is used, an exposure step and During the development process, a pattern is formed using a crosslinking reaction by radical polymerization of the radical polymerizable component, and the resulting pattern is heated to a high temperature in a heating process to cause an imidization reaction, resulting in high heat resistance and high insulation properties. Is formed. As described above, in the case of using the photosensitive composition containing the above-described radically polymerizable component, the reaction is complicated in multiple stages, but by providing the above-described storage step, the microscopic state of the film is stabilized. It is presumed that it was possible to stabilize the properties of the formed film and produce a laminate having excellent adhesion.
Hereinafter, each step in the method for producing a laminate of the present invention will be described.

(Photosensitive resin composition layer forming step)
The method for producing a laminate of the present invention includes a photosensitive resin composition layer forming step of forming a photosensitive resin composition layer by applying the photosensitive resin composition on a support. The photosensitive resin composition will be described later.

  The type of the support can be appropriately determined depending on the use. For example, an inorganic substrate, a resin substrate, a resin composite material substrate, and the like can be given. Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride (silicon nitride) substrate, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is deposited on such a substrate. As the resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamide imide, polyether imide, Polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, fluorine resin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, Group consisting of synthetic resin such as aromatic ether, maleimide, olefin, cellulose, episulfide compound, etc. And the like. These substrates are rarely used as they are in the above-described form, and usually have a multilayer laminated structure such as a thin film transistor (TFT) element depending on the form of the final product. When a photosensitive resin composition layer is further formed on the surface of the photosensitive resin composition layer or the surface of the metal layer, the photosensitive resin composition layer or the metal layer serves as a support.

As a method of applying the photosensitive resin composition to the support, coating is preferable. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, slit scanning, and inkjet printing. You. From the viewpoint of uniformity of the thickness of the photosensitive resin composition layer, spin coating is more preferable. In the case of the spin coating method, for example, a rotation speed of 500 to 2000 rpm can be applied for about 10 seconds to 1 minute.
The thickness of the photosensitive resin composition layer is preferably applied so that the film thickness after exposure is 0.1 to 100 μm, and more preferably 1 to 50 μm. Further, the thickness of the formed photosensitive resin composition layer is not necessarily required to be uniform. For example, when a photosensitive resin composition layer is formed on an uneven surface, the photosensitive resin composition layers may have different thicknesses.

In the photosensitive resin composition layer forming step, the photosensitive resin composition layer formed on the support may be dried. The drying temperature is preferably from 50 to 150C, more preferably from 70 to 130C, even more preferably from 90 to 110C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 to 10 minutes, and still more preferably 3 to 7 minutes. The drying treatment is a step different from the storage step in the present invention.

(Exposure process)
The method for producing a laminate of the present invention includes an exposure step of exposing the photosensitive resin composition layer in a pattern. Exposure is not particularly limited so long as it can cure the photosensitive resin composition, for example, it is preferable to irradiate at 100~10000mJ / cm ² at an exposure energy conversion at a wavelength 365 nm, the 200~8000mJ / cm ² It is more preferable to perform irradiation. The exposure wavelength can be appropriately determined within the range of 190 to 1000 nm, and preferably 240 to 550 nm.

(Development process)
The method for producing a laminate of the present invention includes a developing step of forming a pattern by developing the photosensitive resin composition layer on the exposed photosensitive resin composition layer. Development is performed using a developer. The developer can be used without any particular limitation. Solvents are preferred. Examples of the solvent used for the developer include organic solvents such as esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides. For details of these, the solvents described in the section of the resin composition described later are exemplified.
Among them, 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, propylene glycol methyl ether and propylene glycol methyl ether acetate are preferred, and cyclopentanone and γ-butyrolactone are more preferred.

  The development time is preferably from 10 seconds to 5 minutes. The temperature at the time of development is not particularly limited, but can be 20 to 40 ° C. After the treatment using the developer, rinsing may be further performed. Rinsing is preferably performed with a solvent different from the developer. For example, rinsing can be performed using a solvent contained in the photosensitive resin composition. The rinsing time is preferably from 5 seconds to 1 minute.

(Heating process)
The method for producing a laminate of the present invention includes a heating step of heating a pattern (resin layer) obtained in the developing step. In the heating step, a cyclization reaction of the polyimide precursor and the like proceeds. In addition, curing of unreacted radically polymerizable components also proceeds. The maximum heating temperature (the maximum temperature during heating) is preferably from 100 to 500C, more preferably from 140 to 400C, and still more preferably from 160 to 350C.
Heating is preferably carried out at a rate of 1 to 12 ° C./min from a temperature of 20 to 150 ° C. to a maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the heating rate to 2 ° C./min or more, it is possible to prevent excessive volatilization of the amine while securing high productivity, and it is obtained by setting the heating rate to 12 ° C./min or less. Stress remaining in the film can be reduced.
The temperature at the start of heating is preferably from 20 to 150C, more preferably from 20C to 130C, even more preferably from 25C to 120C. The temperature at the start of heating refers to the heating temperature at the start of the step of heating to the maximum heating temperature. For example, when the photosensitive resin composition is applied on a substrate and then dried, the temperature after drying is, for example, 30 to 200 ° C. lower than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to gradually raise the temperature.
After reaching the maximum heating temperature, heating is preferably performed for 10 to 360 minutes, more preferably for 20 to 300 minutes, and particularly preferably for 30 to 240 minutes.

The heating may be performed stepwise. As an example, the temperature is raised at a rate of 3 ° C./min from 25 ° C. to 180 ° C., and kept at 180 ° C. for 60 minutes, and the temperature is raised at a rate of 2 ° C./min from 180 ° C. to 200 ° C., and kept at 200 ° C. for 120 minutes. And the like.
Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

  The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the polyimide precursor and the like. The oxygen concentration is preferably at most 50 ppm by volume, more preferably at most 20 ppm by volume.

(Metal layer forming step)
The method for producing a laminate of the present invention includes a metal layer forming step of forming a metal layer on a heated pattern (resin layer). The metal layer is not particularly limited, and an existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten, with copper and aluminum being preferred, and copper being more preferred. The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-T-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these are conceivable. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating, may be mentioned.
The thickness of the metal layer at the thickest portion is preferably 0.1 to 50 μm, more preferably 1 to 10 μm.

(Surface activation treatment step)
The method for producing a laminate of the present invention may include a surface activation treatment step of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment. The surface activation treatment may be performed on at least a part of the metal layer, may be performed on at least a part of the photosensitive resin composition layer after the heating step, or may be performed on the metal layer and the photosensitive layer after the heating step. The process may be performed on at least a part of both of the conductive resin composition layers.
The surface activation treatment step is usually performed after the metal layer formation step, but after the heating step, the photosensitive resin composition layer may be subjected to the surface activation treatment step, and then the metal layer may be formed. .
The surface activation treatment is preferably performed on at least a part of the metal layer, and among the metal layers, it is preferable to perform the surface activation treatment on part or all of a region where the photosensitive resin composition layer is formed on the surface. . Thus, by performing the surface activation treatment on the surface of the metal layer, the adhesiveness with the photosensitive resin composition layer layer provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is also performed on part or all of the photosensitive resin composition layer after the heating step. As described above, by performing the surface activation treatment on the surface of the photosensitive resin composition layer, it is possible to improve the adhesion with the metal layer or the photosensitive resin composition layer provided on the surface subjected to the surface activation treatment. .
As the surface activation treatment, plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF ₄ / O ₂ , NF ₃ / O ₂ , a compound having at least one amino group and a thiol group after etching treatment with SF ₆ , NF ₃ , NF ₃ / O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in a hydrochloric acid aqueous solution to remove an oxide film, A plasma treatment is preferable, and a plasma treatment is preferable, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, the energy is preferably 500~200000J / ^{m 2,} more preferably ^{1000~100000J / m 2, 10000~50000J / m} 2 is most preferred.

(Storage process)
The method for producing a laminate according to the present invention includes the steps of: a photosensitive resin composition layer forming step and an exposing step; an exposing step and a developing step; a developing step and a heating step; and a heating step and a metal layer. In at least one of the steps of the forming step, after the surface temperature reaches a certain temperature, a storing step of storing the state for 5 minutes or more is performed. The above-mentioned storage step may be performed in all of the steps, or the storage step may be performed in only one of the steps. In the present invention, the storage step may be performed in at least one of the photosensitive resin composition layer forming step and the exposing step, the exposing step and the developing step, and at least one of the developing step and the heating step. Preferably, a storage step is performed between the exposure step and the development step. By performing the storage step between the exposure step and the development step, the adhesiveness of the photosensitive resin composition layer can be further improved.

  In the present invention, the storage step means a step of storing the surface temperature for 5 minutes or more after the surface temperature reaches a certain temperature. Here, the surface temperature refers to the surface temperature of an object to be processed such as a photosensitive resin composition layer or a pattern (resin layer) formed by the photosensitive resin composition layer.

  In the present invention, the constant temperature in the storage step does not mean a specific temperature, and may have a predetermined temperature range. The fluctuation range of the surface temperature of the object to be processed in the storage step (difference between the maximum value and the minimum value of the surface temperature) is preferably 15 ° C or less, more preferably 10 ° C or less, and more preferably 5 ° C or less. It is even more preferred. When the fluctuation range of the surface temperature is in the above-mentioned range, the properties of the film can be easily stabilized, and a laminate having excellent adhesion can be easily produced.

  In the present invention, the average surface temperature of the object to be treated in the storage step is preferably −30 ° C. or higher, more preferably 4 ° C. or higher, still more preferably 10 ° C. or higher, and particularly preferably 20 ° C. or higher. The upper limit is preferably 100 ° C. or lower, more preferably 60 ° C. or lower, further preferably 45 ° C. or lower, and particularly preferably 30 ° C. or lower. Note that the average surface temperature of the object to be processed means an average of the surface temperatures of the object to be processed for each time. The storage step is performed for 5 minutes or more.

When a storage step is performed between the exposure step and the development step (hereinafter, this storage step is also referred to as a PED (Post Exposure Delay) step), the PED step is preferably performed under conditions that satisfy the following equation.
5 ≦ t1 <( ^{10−0.036 × T1 + 12.3} ) × 60
T1 is the average surface temperature in the PED process, in K; t1 is the time of the PED process, in minutes.

  Further, the average surface temperature of the object to be treated in the PED step is preferably −30 to 60 ° C., more preferably 4 to 45 ° C., and still more preferably 20 to 30 ° C. The PED step is preferably performed for 5 to 720 minutes, more preferably for 5 to 480 minutes, and still more preferably for 5 to 360 minutes. The fluctuation range of the surface temperature of the object in the PED step is preferably 15 ° C. or less, more preferably 10 ° C. or less, and even more preferably 5 ° C. or less.

When a storage step (hereinafter, this storage step is also referred to as a PCD (Post Coating Delay) step) is performed between the photosensitive resin composition layer forming step and the exposure step, the PCD step may be performed under a condition satisfying the following equation. preferable.
5 ≦ t2 <( ^{10−0.031 × T2 + 10.7} ) × 60
T2 is the average surface temperature in the PCD process, in K; t2 is the time of the PCD process, in minutes.

  The average surface temperature of the object to be treated in the PCD step is preferably −30 to 60 ° C., more preferably 4 to 45 ° C., and still more preferably 20 to 30 ° C. Further, the PCD step is preferably performed for 5 to 360 minutes, more preferably for 5 to 120 minutes, and still more preferably for 5 to 60 minutes. The fluctuation range of the surface temperature of the object in the PCD step is preferably 15 ° C. or less, more preferably 10 ° C. or less, and further preferably 5 ° C. or less.

When a storage step (hereinafter, this storage step is also referred to as a PDD (Post Development Delay) step) is performed between the developing step and the heating step, the PDD step is preferably performed under conditions that satisfy the following formula.
5 ≦ t3 <( ^{10−0.02 × T3 + 8.0} ) × 60
T3 is the average surface temperature in the PDD process, in K; t3 is the time of the PDD process, in minutes.

  Further, the average surface temperature of the object to be treated in the PDD step is preferably from 4 to 80 ° C, more preferably from 10 to 60 ° C, even more preferably from 20 to 30 ° C. The PDD step is preferably performed for 5 to 1200 minutes, more preferably for 5 to 720 minutes, further preferably for 5 to 600 minutes, and particularly preferably for 5 to 300 minutes. The fluctuation range of the surface temperature of the object in the PDD step is preferably 30 ° C. or lower, more preferably 20 ° C. or lower, and further preferably 10 ° C. or lower.

  In the case where a storage step (hereinafter, this storage step is also referred to as a PBD (Post Bake Delay) step) is performed between the heating step and the metal layer forming step, the average surface temperature of the object to be processed in the PBD step is 4 to 100 ° C. Is preferably 10 to 80 ° C, more preferably 20 to 60 ° C. The PBD step is preferably performed for 5 to 2400 minutes, more preferably for 5 to 1200 minutes, further preferably for 5 to 900 minutes, and particularly preferably for 5 to 600 minutes. The fluctuation range of the surface temperature of the object in the PBD step is preferably 60 ° C. or lower, more preferably 45 ° C. or lower, and further preferably 30 ° C. or lower.

In the method for producing a laminate of the present invention, a photosensitive resin composition layer forming step, an exposing step, a developing step, a heating step and a metal layer forming step are further performed in this order on the pattern (resin layer) after the metal layer forming step. Performed in, between the photosensitive resin composition layer forming step and the exposing step, between the exposing step and the developing step, between the developing step and the heating step, and at least between the heating step and the metal layer forming step On the one hand, it is also preferable to carry out a series of cycles for performing the preservation step two or more times. The above-described cycle is preferably performed 2 to 7 times, more preferably 2 to 5 times. By doing so, a laminate having a multilayer wiring structure in which a plurality of resin layers and metal layers formed from the photosensitive resin composition layer are alternately laminated can be manufactured.
Further, as the number of laminations is increased, peeling tends to occur at the interface between the metal layer and the resin layer, at the interface between the resin layers, and at the interface between the resin layer and the support. If the number of layers is increased, peeling between the layers hardly occurs. For this reason, the effect of the present invention can be more remarkably obtained.

FIG. 1 is a diagram illustrating an example of a multilayer body having a multilayer wiring structure. In the figure, reference numeral 500 indicates a laminate, reference numerals 201 to 204 indicate resin layers, and reference numerals 301 to 303 indicate metal layers.
A desired pattern is formed on the resin layer 201. For example, this pattern can be formed by negative development, for example. A metal layer 301 is formed on the surface of the resin layer 201. This metal layer 301 is formed so as to cover a part of the surface of the groove 401 formed in the resin layer 201.
On the metal layer 301, a resin layer 202 is formed. A desired pattern is formed on the resin layer 202, and a part of the metal layer 301 is exposed from the resin layer 202. A metal layer 302 is formed on a surface of the resin layer 202. The metal layer 302 is formed so as to cover a part of the surface of the groove 402 formed in the resin layer 202, and is electrically connected to the metal layer 301 exposed from the resin layer 202.
On the metal layer 302, a resin layer 203 is formed. A desired pattern is formed on the resin layer 203, and a part of the metal layer 302 is exposed from the resin layer 203. On the surface of the resin layer 203, a metal layer 303 is formed. The metal layer 303 is formed so as to cover a part of the surface of the groove 403 formed in the resin layer 203, and is electrically connected to the metal layer 302 exposed from the resin layer 203.
On the metal layer 303, a resin layer 204 is formed. A desired pattern is formed on the resin layer 204, and a part of the metal layer 303 is exposed from the resin layer 204. In FIG. 1, a part of the metal layer 302 is also exposed from the resin layer 204.
In this laminate, the resin layers 201 to 204 function as insulating films, and the metal layers 301 to 303 function as wiring layers. Such a laminate can be preferably used as a rewiring layer in an electronic device.

<Photosensitive resin composition (resin composition)>
Next, a photosensitive resin composition (hereinafter, also referred to as a resin composition) used in the method for producing a laminate of the present invention will be described.

<< Resin >>
The resin composition in the present invention contains a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. When a polyimide precursor or a polybenzoxazole precursor is used as the resin, the properties of the film tend to be less stable. For this reason, when the polyimide precursor or the polybenzoxazole precursor is used as the resin, the effects of the present invention are particularly easily obtained. In particular, when a polyimide precursor (preferably, a polyimide precursor having a radical polymerizable group) is used as the resin, the effects of the present invention are more likely to be obtained more remarkably.

The content of the resin in the resin composition is preferably from 20 to 99% by mass, more preferably from 50 to 99% by mass, still more preferably from 60 to 99% by mass, and more preferably from 70 to 99% by mass, based on the total solid content of the resin composition. Is particularly preferred.
Further, the content of the polyimide precursor in the resin composition is preferably from 20 to 99% by mass, more preferably from 50 to 99% by mass, still more preferably from 60 to 99% by mass, based on the total solid content of the resin composition. 70-99 mass% is particularly preferred.
Further, the content of the polyimide precursor in the total mass of the resin contained in the resin composition is preferably from 80 to 100% by mass, and more preferably from 90 to 100% by mass. It is preferable that the resin contained in the resin composition is substantially composed of only the polyimide precursor. When the resin contained in the resin composition is substantially composed of only the polyimide precursor, for example, the content of the resin other than the polyimide precursor contained in the resin composition is the content of the polyimide precursor Is preferably 3% by mass or less.

(Polyimide precursor)
The polyimide precursor is preferably a polyimide precursor containing a repeating unit represented by the formula (1).
Equation (1)
In the formula (1), A ²¹ and A ²² each independently represent an oxygen atom or —NH—, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group.

A ²¹ and A ²² each independently represent an oxygen atom or —NH—, and an oxygen atom is preferable.

R ²¹ represents a divalent organic group. Examples of the divalent organic group include a group containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aryl group, and include a linear or branched aliphatic group having 2 to 20 carbon atoms, and a carbon group having 6 carbon atoms. A cyclic aliphatic group having from 20 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, or a group comprising a combination thereof is preferred, and a group comprising an aryl group having from 6 to 20 carbon atoms is more preferred. Examples of the aryl group include the following.

In the formula, A is a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C (= O)-, -S-, -S (= O) 2 _- and -NHCO-, and is preferably a group selected from combinations thereof, a single bond, an optionally substituted alkylene group having 1 to 3 carbon atoms by fluorine atoms, -O -, - C (= O) -, - S -, - SO 2 - , more preferably a group selected _{from, -CH 2 -, - O -} , - S -, - SO 2 -, - C (CF 3 _{) 2 -, - C (CH} 3) 2 - and more preferably a divalent group selected from.

Specifically, R ²¹ includes a diamine residue remaining after removal of an amino group of the following diamine.
1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 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- and p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4′- and 3,3′-diaminodiphenylether, 4,4′- and 3,3′-diaminodiphenylmethane, 4, '-And 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- and 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-aminophenyl) 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′-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3′-diethyl-4,4′-diamino Phenylmethane, 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, 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'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diamid Nodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6 -Trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide , Diaminobenzoic acid ester, 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-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-trifluoromethylf Noxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoro Propane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'- At least one diamine selected from bis (trifluoromethyl) biphenyl, 2,2 ′, 5,5 ′, 6,6′-hexafluorotrizine and 4,4 ″ ′-diaminoquaterphenyl.

Further, the diamine residues remaining after removal of the amino groups of the diamine shown below (DA-1) ~ (DA -18) may also be mentioned as examples of ^{R 21.}

Further, the diamine residues remaining two or more alkylene glycol units after the removal of the amino groups of the diamine having the main chain may also be mentioned as examples of R ^21. Preferably, it is a diamine residue containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and more preferably a diamine residue containing no aromatic ring. Examples include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( The above product names, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propane) -2-yl) oxy) propan-2-amine, but is not limited thereto. The structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

  In the above, x, y, and z are average values.

In Formula (1), R ²² represents a tetravalent organic group, and is preferably a tetravalent group containing an aromatic ring, and is a group represented by the following Formula (1-1) or Formula (1-2). Is more preferred.

Formula (1-1)
In the formula (1-1), R ¹¹² is a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, —O—, —CO—, —S—, —SO ₂ - and -NHCO-, and is preferably a group selected from combinations thereof, a single bond, or, an optionally substituted alkylene group having 1 to 3 carbon atoms by fluorine atoms, -O -, - CO -, - S- and -SO ₂ -, more preferably a divalent group selected _{from, -CH 2 -, - C (} CF 3) 2 -, - C (CH 3) 2 -, - O -, - CO -, - S- and -SO ₂ - 2 divalent radical selected from the group consisting of is more preferable.

Formula (1-2)

R ²² is such tetracarboxylic acid residue remaining after removal of the anhydride groups from a tetracarboxylic acid dianhydride. Specific examples include the following tetracarboxylic acid residues remaining after removing the acid anhydride groups from the following tetracarboxylic dianhydrides.
Pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethanetetracarboxylic dianhydride 2,2 ', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetra Carboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2 , 2-bis (3,4-dica) Boxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3 -Diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic Acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Anhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarbo (Ciphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and at least one selected from alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms. Species of tetracarboxylic dianhydride.

Also, tetracarboxylic acid residue remaining tetracarboxylic dianhydride represented by the following from (DAA-1) ~ (DAA -5) after removal of the anhydride groups, and as examples of R ^22.

From the viewpoint of solubility in an alkali developer, R ²² preferably has an OH group. More ^{specifically,} as ^{R 22,} tetracarboxylic acid residue remaining after removal of the anhydride groups from the (DAA-1) ~ (DAA -5) can be mentioned.

In the formula (1), R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group represented by R ²³ and R ²⁴ include a linear or branched alkyl group, a cyclic alkyl group, a group containing an aromatic group, and a radical polymerizable group. In the present invention, at least one of R ²³ and R ²⁴ is preferably a group containing a radical polymerizable group. According to this aspect, the effect of the present invention tends to be more remarkably obtained. Further, the photosensitive resin composition containing the polyimide precursor can be preferably used as a negative photosensitive resin composition. Examples of the radical polymerizable group include a group having an ethylenically unsaturated bond. Specific examples of the radical polymerizable group include a vinyl group, a (meth) allyl group, and a group represented by the following formula (III).

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
In Formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH (OH) CH ₂ —, or a polyoxyalkylene group having 4 to 30 carbon atoms. Examples of suitable R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene. _{group, -CH 2 CH (OH) CH} 2 - and the like, ethylene group, propylene group, trimethylene _{group, -CH 2 CH (OH) CH} 2 - is more preferable. Combinations wherein R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group are particularly preferred.

The linear or branched alkyl group preferably has 1 to 30 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, Examples include a sec-butyl group, a t-butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group.
The cyclic alkyl group may be a monocyclic alkyl group or a polycyclic alkyl group. Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alkyl group include, for example, an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. No. Above all, a cyclohexyl group is preferable from the viewpoint of compatibility with high sensitivity.
As the aromatic group, a substituted or unsubstituted benzene ring group, naphthalene ring group, pentalene ring group, indene ring group, azulene ring group, heptalene ring group, indacene ring group, perylene ring group, pentacene ring group, acenaphthene ring group , Phenanthrene ring group, anthracene ring group, naphthacene ring group, chrysene ring group, triphenylene ring group, fluorene ring group, biphenyl ring group, pyrrole ring group, furan ring group, thiophene ring group, imidazole ring group, oxazole ring group, thiazole Ring group, pyridine ring group, pyrazine ring group, pyrimidine ring group, pyridazine ring group, indolizine ring group, indole ring group, benzofuran ring group, benzothiophene ring group, isobenzofuran ring group, quinolidine ring group, quinoline ring group, Phthalazine ring group, naphthyridine ring group, quinoxaline ring group, quinoxazoline ring group, iso A norin ring group, a carbazole ring group, a phenanthridine ring group, an acridine ring group, a phenanthroline ring group, a thianthrene ring group, a chromene ring group, a xanthene ring group, a phenoxatiin ring group, a phenothiazine ring group or a phenazine ring group. . Benzene ring groups are preferred.

In the formula (1), when A ²² is an oxygen atom and R ²³ is a hydrogen atom, and / or when A ²¹ is an oxygen atom and R ²⁴ is a hydrogen atom, the polyimide precursor is ethylenically non-functional. A tertiary amine compound having a saturated bond may form a counter salt. Examples of such a tertiary amine compound having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

  In the case of alkali development, the polyimide precursor preferably has a fluorine atom in a structural unit from the viewpoint of improving resolution. The fluorine atom imparts water repellency to the surface of the film during alkali development, and can suppress infiltration from the surface. The fluorine atom content in the polyimide precursor is preferably at least 10% by mass, and from the viewpoint of solubility in an aqueous alkaline solution, is preferably at most 20% by mass.

  Further, for the purpose of improving the adhesion to the substrate, the polyimide precursor may copolymerize an aliphatic group having a siloxane structure. Specifically, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like can be given as the diamine component.

  In addition, to improve the storage stability of the resin composition, the main chain terminal of the polyimide precursor is sealed with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Is preferred. Among these, it is more preferable to use a monoamine. Preferred compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, and 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, 2-aminobenzoic acid, 3- Minobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino- Examples thereof include 4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

The polyimide precursor may be composed of a repeating unit represented by the formula (1) and another repeating unit that is another polyimide precursor.
When another repeating unit is contained, the proportion of the other repeating unit in the polyimide precursor is preferably from 1 to 60 mol%, more preferably from 5 to 50 mol%.

  The polyimide precursor in the present invention may have a configuration substantially free of other polyimide precursors other than the polyimide precursor containing the repeating unit represented by the formula (1). The term "substantially not contained" means that, for example, the content of the other polyimide precursor contained in the resin composition is 3% by mass or less of the content of the polyimide precursor.

  The weight average molecular weight (Mw) of the polyimide precursor is preferably 20,000 to 28,000, more preferably 22,000 to 27,000, and further preferably 23,000 to 25,000. The degree of dispersion (Mw / Mn) of the polyimide precursor is not particularly limited, but is preferably 1.0 or more, more preferably 2.5 or more, and further preferably 2.8 or more. preferable. Although the upper limit of the degree of dispersion of the polyimide precursor is not particularly limited, it is preferably, for example, 4.5 or less, and may be 3.4 or less.

(Polyimide)
The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, and is preferably a compound represented by the following formula (4), and is represented by the following formula (4). More preferably, the compound is a compound having a radical polymerizable group. Examples of the radical polymerizable group include the polymerizable groups described above for the polyimide precursor, and the preferable range is also the same.
Equation (4)
In the formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

When the polyimide has a radical polymerizable group, a radical polymerizable group may be introduced into at least one of R ¹³¹ and R ¹³² , or as shown in the following formula (4-1) or formula (4-2). A radical polymerizable group may be introduced at the terminal of the polyimide.
Formula (4-1)
In the formula, R ¹³³ is a radical polymerizable group, and the other groups have the same meaning as in formula (4).
Formula (4-2)
In the formula, at least one of R ¹³⁴ and R ¹³⁵ is a radical polymerizable group, the other is an organic group, and the other groups have the same meaning as in formula (4).

Examples of the divalent organic group represented by R ¹³¹ include the same groups as R ²¹ in Formula (1) of the polyimide precursor described above, and the preferable range is also the same. Examples of the tetravalent organic group represented by R ¹³² include the same groups as R ²² in Formula (1) of the polyimide precursor described above, and the preferable range is also the same.

  The polyimide preferably has an imidization ratio of 85% or more, more preferably 90% or more. When the imidation ratio is 85% or more, film shrinkage due to ring closure that occurs when imidization is performed by heating is reduced, and occurrence of warpage can be suppressed.

Polyimide, In addition to all the repeating structural units of the formula based on one ^{R 131} or ^{R 132} (4), may include a repeating unit containing two or more different types of ^{R 131} or ^{R 132.} Further, the polyimide may include other types of repeating structural units in addition to the repeating unit of the above formula (4).

Polyimide can be prepared by, for example, reacting a tetracarboxylic dianhydride with a diamine compound (partially substituted with a terminal capping agent which is a monoamine) at a low temperature, or a tetracarboxylic dianhydride (partially using an acid at a low temperature). A method of reacting an anhydride or a terminal blocking agent which is a monoacid chloride compound or a monoactive ester compound) with a diamine compound, obtaining a diester with tetracarboxylic dianhydride and an alcohol, and then diamine (partially monoamine). Reaction with a terminal capping agent) in the presence of a condensing agent, a diester is obtained with tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorided, and a diamine (partially monoamine) is obtained. The polyimide precursor is obtained by a method such as a method of reacting with a terminal capping agent which is a A method of completely imidizing using a domination reaction method, or a method of stopping an imidation reaction in the middle and partially introducing an imide structure, and further blending a fully imidized polymer with its polyimide precursor By doing so, it is possible to synthesize using a method of partially introducing an imide structure.
Examples of commercially available polyimides include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN).

  The weight average molecular weight (Mw) of the polyimide is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, and particularly preferably from 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breaking resistance of the cured film can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. When two or more kinds of polyimides are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is within the above range.

(Polybenzoxazole precursor)
In the present invention, the structure of the polybenzoxazole precursor is not particularly limited, but is preferably a compound containing a repeating unit represented by the following formula (3).
Equation (3)
In the formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. Represent.

In the formula (3), R ¹²³ and R ¹²⁴ have the same meanings as R ²³ in the formula (1), and the preferred range is also the same.

In the formula (3), the divalent organic group represented by R ¹²¹ is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. As the dicarboxylic acid, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are preferable, and a dicarboxylic acid containing an aromatic group is more preferable.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferable, and a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group and two COOHs is used. Are more preferred. The straight-chain or branched (preferably straight-chain) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, still more preferably 3 to 20 carbon atoms. It is particularly preferably 15 and more preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Specific examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, and methylsuccinic acid. 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethyl Glutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeline Acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-no Diacid, dodecandioic acid, tridecandioic acid, tetradecandioic acid, pentadecandioic acid, hexadecandioic acid, heptadecandioic acid, octadecandioic acid, nonadecandioic acid, eicosanediacid, heneicosandioic acid, docosanedioic acid, tricosandioic acid Acid, tetracosantioic acid, pentacosantioic acid, hexacosantioic acid, heptacosantioic acid, octakosantioic acid, nonacosantioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and the following formula And the like.

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

  As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferable, and a dicarboxylic acid consisting of only the following aromatic group and two COOHs is more preferable.

In the formula, A _{-CH 2 -, - O -,} - S -, - SO 2 -, - CO -, - NHCO -, - C (CF 3) 2 -, and, -C (CH _{3) 2} - Represents a divalent group selected from the group consisting of

  As specific examples of the dicarboxylic acid containing an aromatic group, 4,4'-carbonyldibenzoic acid and 4,4'-dicarboxydiphenyl ether terephthalic acid are preferable.

In the formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group include the groups described in R ²² in the formula (1), and preferred ranges are also the same.

  The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29000, and still more preferably 22000 to 28000. Further, the number average molecular weight (Mn) is preferably from 7200 to 14000, more preferably from 8000 to 12000, and still more preferably from 9200 to 11200. The degree of dispersion of the polybenzoxazole precursor is preferably at least 1.4, more preferably at least 1.5, and even more preferably at least 1.6. The upper limit of the degree of dispersion of the polybenzoxazole precursor is not particularly limited, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, still more preferably 2.4 or less, and more preferably 2.3 or less. It is more preferably 2.2 or less.

(Polybenzoxazole)
The polybenzoxazole is not particularly limited as long as it is a compound having a benzoxazole ring, and is preferably a compound having a repeating unit represented by the following formula (X), and represented by the following formula (X) And more preferably a compound having a radical polymerizable group. Examples of the radical polymerizable group include the radical polymerizable groups described in the above polyimide precursor, and the preferable range is also the same.
In the formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.

When the polybenzoxazole has a radically polymerizable group, a radically polymerizable group may be introduced into at least one of R ¹³³ and R ¹³⁴ , as shown in the following formula (X-1) or (X-2). May have a radical polymerizable group introduced into the terminal of polybenzoxazole.
Formula (X-1)
In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a radical polymerizable group, the other is an organic group, and the other groups have the same meaning as in formula (X).
Formula (X-2)
In the formula (X-2), R ¹³⁷ is a radical polymerizable group, the other is a substituent, and the other groups are as defined in the formula (X).

^Examples of the divalent organic group represented by R ¹³³ include an aliphatic or aromatic group. Specific examples include the groups described for ^R121 in the formula (3) of the polybenzoxazole precursor, and the preferable range is also the same.

^Examples of the tetravalent organic group represented by R ¹³⁴ include the groups described for R ¹²² in the formula (3) of the polybenzoxazole precursor, and the preferable range is also the same.

Polybenzoxazoles, In addition to all the repeating structural unit represented by the above formula (X) based on one of ^{R 133} or ^{R 134,} the above formula comprising two or more different types of ^{R 133} or ^{R 134} (X ) May be included. Further, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating unit of the above formula (X).

Polybenzoxazole may, for example, a bis-aminophenol derivative, a dicarboxylic acid and is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives of the dicarboxylic acids polybenzoxazole precursor including R ^133, which By using a known oxazole-forming reaction method. In the case of dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield and the like.

  The weight average molecular weight (Mw) of polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, and particularly preferably from 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breaking resistance of the cured film can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is more preferably 20,000 or more. When two or more polybenzoxazoles are contained, the weight average molecular weight of at least one polybenzoxazole is preferably within the above range.

<< radical polymerizable compound >>
The resin composition in the present invention may further contain a radical polymerizable compound. By containing a radical polymerizable compound, it can be preferably used as a negative photosensitive resin composition. Further, a cured film having excellent heat resistance can be formed. As the radical polymerizable compound, a compound having an ethylenically unsaturated bond is preferable, and a compound having two or more groups having an ethylenically unsaturated bond is more preferable. The radically polymerizable compound may be in any of chemical forms such as, for example, monomers, prepolymers, oligomers and mixtures thereof and multimers thereof. As the group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable. The radical polymerizable compound in the present invention is a component different from the above-mentioned resin. That is, a polyimide precursor having a radical polymerizable group, a polyimide having a radical polymerizable group, a polybenzoxazole precursor having a radical polymerizable group, and a polybenzoxazole having a radical polymerizable group correspond to the resin.

In the present invention, a monomer type radical polymerizable compound (hereinafter, also referred to as a radical polymerizable monomer) is a compound different from a polymer compound. The radical polymerizable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and a low molecular compound having a molecular weight of 900 or less. More preferably, it is a compound. Incidentally, the molecular weight of the radical polymerizable monomer is usually 100 or more.
The oligomer-type radical polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 radical polymerizable monomers are bonded. As the molecular weight, the weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and still more preferably 2,000 to 10,000.

  The number of functional groups of the radically polymerizable compound in the present invention means the number of radically polymerizable groups in one molecule. From the viewpoint of resolution, the resin composition preferably contains at least one kind of bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and at least 1 to 2 to 4 functional radical polymerizable compounds. More preferably, it contains species.

  Examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof. Esters of acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, A dehydration-condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and further, a halogen group Also preferred are substitution products of unsaturated carboxylic acid esters or amides having a leaving substituent such as thiol or a tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols. Further, as another example, it is also possible to use a group of compounds in which unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the above unsaturated carboxylic acid. As specific examples, descriptions in paragraphs 0113 to 0122 of JP-A-2006-027357 can be referred to, and the contents thereof are incorporated in the present specification.

  As the radical polymerizable compound, a compound having a boiling point of 100 ° C. or more under normal pressure is also preferable. Examples 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 (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol, and then (meth) acrylated, JP-B-48-4170 , Urethane (meth) acrylates described in JP-B-50-6034 and JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, and JP-A-49-43191. Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-30490, epoxy acrylates which are reaction products of epoxy resins with (meth) acrylic acid, and mixtures thereof. it can. Further, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.

  Examples of the radical polymerizable compound include a group having a fluorene ring and having an ethylenically unsaturated bond described in JP-A-2010-160418, JP-A-2010-129825, and JP-A-4364216. It is also possible to use compounds having more than one compound and cardo resins. Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And the like. Further, a compound containing a perfluoroalkyl group described in JP-A-61-22048 can also be used. Further, the Journal of the Adhesion Society of Japan vol. 20, no. 7, pages 300 to 308 (1984) as photopolymerizable monomers and oligomers can also be used.

  In addition to the above, compounds represented by the following formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In each of the above formulas, n is an integer of 0 to 14, and m is an integer of 0 to 8. A plurality of R and T in the molecule may be the same or different.
In each of the above formulas (MO-1) ~ compounds represented by (MO-5), at least one of the plurality of R may, -OC (= O) CH = CH 2, or, -OC (= O) represents a group represented by C (CH ₃ ) ＝ CH ₂ .
Specific examples of the compounds represented by the above formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of JP-A-2007-269779.

  Further, compounds described in formula (1) and formula (2) in JP-A-10-62986 together with specific examples thereof, which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, It can be used as a radical polymerizable compound. Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187221 can also be used as radically polymerizable compounds, the contents of which are incorporated herein.

  Examples of the radical polymerizable compound include dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercially available product; Nippon Kayaku ( A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (KAYAARD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) Acrylates (KAYARAD DPHA as commercial products; Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups bonded via ethylene glycol and propylene glycol residues Is preferred. These oligomer types can also be used. Further, pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formulas (MO-1) and (MO-2) are also preferable examples. In addition, SR209 manufactured by Sartomer can be used.

  The radically polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, and a phosphoric acid group. Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520. The preferred acid value of the radical polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the above compound is in the above range, it is excellent in production and handleability, and further excellent in developability. Further, the radical polymerizability is good.

  As the radical polymerizable compound, a compound having a caprolactone structure can also be used. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, Ε-caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. Can be. Among them, a compound represented by the following formula (C) is preferable.

Formula (C)

  In the formula, all six Rs are groups represented by the following formula (D), or 1 to 5 of the six Rs are groups represented by the following formula (D), Is a group represented by the following formula (E).

Formula (D)

In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2, and “*” represents a bond.

Formula (E)

In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.

Such a compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, for example, DPCA-20 (m = 1 in the above formulas (C) to (E), formula (D) = 2, compounds in which all R ¹ are hydrogen atoms), DPCA-30 (same formula, m = 1, number of groups represented by formula (D) = 3, R ¹ is all A compound which is a hydrogen atom), DPCA-60 (the same formula, m = 1, the number of groups represented by the formula (D) = 6, a compound in which all R ¹ are hydrogen atoms), DPCA-120 (in the same formula, m = 2, the number of groups represented by the formula (D) = 6, and compounds in which all R ¹ are hydrogen atoms.

  The radical polymerizable compound is also preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the formulas (i) and (ii), E independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-, y each independently represents an integer of 0 to 10, and X each independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the formula (i), the total number of the (meth) acryloyl groups is 3 or 4, and m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. However, when the sum of each m is 0, any one of X is a carboxyl group.
In the formula (ii), the total number of the (meth) acryloyl groups is 5 or 6, and n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the sum of each n is 0, any one of X is a carboxyl group.

In the formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In the formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. In addition, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In the formula (i) or the formula (ii),-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-has an oxygen atom-side terminal bonded to X. Is preferred. In particular, in the formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  Commercially available products of the compounds represented by the formulas (i) and (ii) include, for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and pentylene manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains, are exemplified.

Examples of the radical polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, use of addition polymerizable monomers having an amino structure or a sulfide structure in a molecule described in JP-A-63-277563, JP-A-63-260909, and JP-A-1-105238. You can also.
As commercially available products, urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.) And Blemmer PME400 (manufactured by NOF Corporation).

  The radical polymerizable compound preferably has a partial structure represented by the following formula from the viewpoint of heat resistance. However, * in the formula is a connecting hand.

  Specific examples of the compound having the above partial structure include, for example, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. ) Acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, etc. .

In the resin composition, the content of the radical polymerizable compound is preferably 1 to 50% by mass based on the total solid content of the resin composition from the viewpoint of good radical polymerizability and heat resistance. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less.
In addition, the mass ratio (resin / radical polymerizable compound) of the resin (preferably the polyimide precursor) and the radical polymerizable compound is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, 90/10 to 50/50 are more preferred. When the mass ratio of the resin and the radical polymerizable compound is in the above range, a cured film having excellent curability and heat resistance can be formed. Only one radical polymerizable compound may be used, or two or more radical polymerizable compounds may be used. When two or more kinds are used, the total amount is preferably within the above range.

<< Photopolymerization initiator >>
The resin composition in the present invention contains a photopolymerization initiator. Examples of the photopolymerization initiator include a photocationic polymerization initiator and a photoradical polymerization initiator, and a photoradical polymerization initiator is preferable. After the resin composition in the present invention contains a photo-radical polymerization initiator, a resin composition layer is formed by applying the resin composition to a substrate such as a semiconductor wafer, and then irradiated with light to cause a radical. Curing occurs, and the solubility in the light irradiation part can be reduced. For this reason, for example, by exposing the resin composition layer through a photomask having a pattern that masks only the electrode portion, there is an advantage that regions having different solubility can be easily formed according to the pattern of the electrodes and the like. .

  The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. In addition, an activator that produces some action with the photoexcited sensitizer and generates an active radical may be used. The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

  As the photopolymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (eg, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. No. For these details, the description of paragraphs 0165 to 182 of JP-A-2006-027357 can be referred to, and the contents thereof are incorporated herein. Examples of the ketone compound include, for example, compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, Kayacure DETX (produced by Nippon Kayaku Co., Ltd.) is also suitably used.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound and a metallocene compound can also be suitably used. More specifically, for example, a photopolymerization initiator described in JP-A-10-291969 and a photopolymerization initiator described in Japanese Patent No. 4225988 can also be used.
As the α-hydroxyketone compound, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all trade names: manufactured by BASF) can be used.
As the α-aminoketone compound, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names, all manufactured by BASF) can be used. As the α-aminoketone compound, a compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used.
Examples of the acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

An oxime compound is more preferably used as the photopolymerization initiator. By using the oxime compound, the exposure latitude can be more effectively improved. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a thermal base generator.
As specific examples of the oxime compound, the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166 can be used. Preferred oxime compounds include, for example, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimiminobtan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one.

Commercial products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF) and Adeka Optomer N-1919 (available from ADEKA CORPORATION, JP 2012-14052A). The polymerization initiator 2) is also preferably used. Also, TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Aquel's NCI-831 and Adeka Aquel's NCI-930 (manufactured by ADEKA) can be used. Alternatively, DFI-091 (manufactured by Daito Mix) can be used. Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013 And the compound (C-3) described in paragraph 0101 of JP-A-164471.
The most preferred oxime compounds include oxime compounds having a specific substituent described in JP-A-2007-269779, oxime compounds having a thioaryl group described in JP-A-2009-191061, and the like.

  As the photopolymerization initiator, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl At least one selected from imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, halomethyloxadiazole compound, and 3-aryl-substituted coumarin compound One is preferable, and a trihalomethyltriazine compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide Compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound and an acetophenone compound, more preferably at least one selected from the group consisting of a trihalomethyltriazine compound, an α-hydroxyketone compound, an α-aminoketone compound, and an oxime. At least one selected from a compound, a triarylimidazole dimer and a benzophenone compound is more preferred, a metallocene compound or an oxime compound is still more preferred, and an oxime compound is particularly preferred.

The photopolymerization initiator may be N, N'-tetraalkyl-4,4'-diaminobenzophenone such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl- Aromatic ketones such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, and alkylanthraquinone; Quinones condensed with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal can also be used. Further, a compound represented by the following formula (I) can also be used.
In the formula (I), R ⁵⁰ is an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by at least one oxygen atom; an alkoxy group having 1 to 12 carbon atoms; a phenyl group; C1-C20 alkyl group, C1-C12 alkoxy group, halogen atom, cyclopentyl group, cyclohexyl group, C2-C12 alkenyl group, C2-C2 interrupted by one or more oxygen atoms A phenyl group substituted with at least one of an alkyl group having 18 and an alkyl group having 1 to 4 carbon atoms; or biphenylyl, wherein R ⁵¹ is a group represented by the formula (II) or the same as R ⁵⁰ R ^{52 to} R ⁵⁴ are each independently alkyl having 1 to 12 carbons, alkoxy or halogen having 1 to 12 carbons.
In the formula, R ^{55 to} R ⁵⁷ are the same as R ^{52 to} R ^{54 in} the above formula (I).

  Further, as the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication WO2015 / 125469 can also be used.

  The content of the photopolymerization initiator is preferably from 0.1 to 30% by mass, more preferably from 0.1 to 20% by mass, and still more preferably from 0.1 to 10% by mass, based on the total solid content of the resin composition. %. The photopolymerization initiator may contain only one kind or two or more kinds. When two or more photopolymerization initiators are contained, the total is preferably within the above range.

<< polymerization inhibitor >>
The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p-benzoquinone, diphenyl-p-benzoquinone, and 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N -Phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso − -Naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4 -Hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication WO2015 / 125469 can also be used.

  When the resin composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass based on the total solid content of the resin composition. The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more polymerization inhibitors, the total is preferably within the above range.

<< Photobase generator >>
The resin composition of the present invention may contain a photobase generator. A photobase generator is a substance that generates a base upon exposure to light and does not show activity under normal conditions of normal temperature and normal pressure. ) Is not particularly limited as long as it generates). Since the base generated by the exposure acts as a catalyst when the polyimide precursor is cured by heating, it can be suitably used in the negative photosensitive resin composition.

  The content of the photobase generator is not particularly limited as long as it can form a desired pattern, and may be a general content. The content of the photobase generator is preferably in the range of 0.01 part by mass or more and less than 30 parts by mass with respect to 100 parts by mass of the resin composition, and in the range of 0.05 parts by mass to 25 parts by mass. Is more preferable, and even more preferably within the range of 0.1 to 20 parts by mass.

  In the present invention, a compound known as a photobase generator can be used. For example, M. Shirai, and M.S. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, Polymer Processing, 46, 2 (1997); Kutal, Coord. Chem. Rev .. , 211, 353 (2001); Kaneko, A .; Sarker, and D.S. Neckers, Chem. Mater. H., 11, 170 (1999); Tachi, M .; Shirai, and M.S. Tsunooka, J .; Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J. et al. Photopolym. Sci. Technol. , 3,419 (1990); Tsunooka, H .; Tachi, and S.M. Yoshitaka, J .; Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H .; Araki, M .; Shirai, J .; Photopolym. Sci. Technol. , 19, 81 (2006), a transition metal compound complex, a compound having a structure such as an ammonium salt, or a compound in which an amidine moiety is latentized by forming a salt with a carboxylic acid. A nonionic compound in which a base component is latentized by a urethane bond or an oxime bond such as an ionic compound or a carbamate derivative, an oxime ester derivative, or an acyl compound, wherein the base component is neutralized by forming a salt. Can be mentioned. It is also preferable to use WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.).

The basic substance generated from the photobase generator is not particularly limited, and examples thereof include a compound having an amino group, in particular, a monoamine, a polyamine such as a diamine, and an amidine.
The generated basic substance is preferably a compound having an amino group having a higher basicity. This is because the catalyst has a strong catalytic action on the dehydration-condensation reaction and the like in the imidation of the polyimide precursor, and the addition of a smaller amount enables the manifestation of the catalytic effect on the dehydration-condensation reaction and the like at a lower temperature. That is, since the generated basic substance has a large catalytic effect, the apparent sensitivity of the resin composition is improved. Amidines and aliphatic amines are preferred from the viewpoint of the above catalytic effect.

  The photobase generator is preferably a photobase generator that does not contain a salt in the structure. It is preferable that there is no charge on the nitrogen atom of the base moiety generated in the photobase generator. In the photobase generator, the generated base is preferably latentized using a covalent bond, and the base generation mechanism is such that the covalent bond between the nitrogen atom of the generated base portion and an adjacent atom is cleaved. More preferably, the compound generates a base. When the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is good and the pot life is improved. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

  Further, for the above-described reason, it is preferable that the photobase generator has the base generated as described above latentified using a covalent bond. Further, it is more preferable that the generated base is latentized using an amide bond, a carbamate bond or an oxime bond.

  Examples of the photobase generator include a photobase generator having a cinnamic acid amide structure described in JP-A-2009-80452 and WO2009 / 123122, JP-A-2006-189591, and JP-A-2008-247747. Photobase generators having a carbamate structure described in the gazette, oxime structures described in JP-A-2007-249013 and JP-A-2008-003581, and photobase generators having a carbamoyloxime structure can also be used. .

  In addition, as the photobase generator, compounds described in JP-A-2012-93746, paragraphs 0185 to 0188, 0199 to 0200 and 0202, compounds described in paragraphs 0022 to 0069 of JP-A-2013-194205 And compounds described in paragraph Nos. 0026 to 0074 of JP2013-204019A, and paragraph 0052 of WO2010 / 064631.

<< thermal base generator >>
The resin composition in the present invention may include a thermal base generator. Examples of the thermal base generator include at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion of 0 to 4 and an ammonium cation. Thermal base generators are preferred. Here, pKa1 indicates the logarithmic representation (−Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can promote the cyclization reaction of the polyimide precursor and the like, and can reduce the ring of the polyimide precursor and the like. Can be performed at low temperature. In addition, even if these compounds are coexisted with a polyimide precursor or the like which is cyclized and cured by a base, the cyclization of the polyimide precursor and the like hardly proceeds unless heated, so that a resin composition having excellent storage stability Can be prepared.
In the present specification, an acidic compound refers to a compound obtained by collecting 1 g of a compound in a container, adding 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio: water / tetrahydrofuran = 1/4), and adding the compound for 1 hour at room temperature. Stirring means a compound having a pH value of less than 7 as measured at 20 ° C. using a pH meter.

The base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, and more preferably 120 to 200 ° C. The upper limit of the base generation temperature is more preferably 190 ° C or lower, further preferably 180 ° C or lower, and further preferably 165 ° C or lower. The lower limit of the base generation temperature is more preferably 130 ° C. or higher, and further preferably 135 ° C. or higher.
When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, a base is hardly generated during storage, so that a resin composition having excellent stability can be prepared. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor can be lowered. The base generation temperature is measured by, for example, differential scanning calorimetry, heating the compound in a pressure-resistant capsule at 250C at 5C / min, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.

  The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since the tertiary amine has a high basicity, the cyclization temperature of the polyimide precursor can be lowered. Further, the boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and most preferably 140 ° C. or higher. The molecular weight of the generated base is preferably from 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of molecular weight is a theoretical value obtained from the structural formula.

  The acidic compound (A1) preferably contains at least one selected from an ammonium salt and a compound represented by the formula (A1) described below.

  The ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.) or 40 ° C. or higher (preferably 120 to 200 ° C.). Compounds other than the acidic compound which generates a base when heated to the above step may be used.

In the present invention, the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or (102) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation. In addition, that the anion exists outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded through a covalent bond. Hereinafter, an anion outside the molecule of the cation portion is also referred to as a counter anion.
In the above formula, R ^{1 to} R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and formula R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁷ may be respectively bonded to form a ring.

In the present invention, the ammonium salt preferably has an anion having a pKa of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is preferably 3.5 or less, more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, and even more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polyimide precursor and the like can be cyclized at a low temperature, and further, the stability of the resin composition can be improved. When the pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the resin composition is good. When pKa1 is 0 or more, the generated base is hardly neutralized, and the cyclization efficiency of the polyimide precursor or the like is good.
The type of the anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion and a sulfate anion, and more preferably a carboxylate anion because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylate anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to provide a thermal base generator that can further improve the stability, curability, and developability of the resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability and developability of the resin composition can be further improved.
In the present invention, the carboxylate anion is preferably a carboxylate anion having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, even more preferably 3.2 or less. According to this aspect, the stability of the resin composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of an acid, and is determined by Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafliger, O.D. FC; Compilation: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, R.M.O.f .; , Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using ACD / pKa (manufactured by ACD / Labs) software will be used.

In the present invention, the carboxylate anion is preferably represented by the following formula (X1).
In the formula (X1), EWG represents an electron-withdrawing group.

In the present invention, the electron-withdrawing group means a group having a positive Hammett's substituent constant σm. Here, σm is a review by Yuho Tsuno, Journal of the Society of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. 631-642. In addition, the electron withdrawing group of the present invention is not limited to the substituents described in the above documents.
Examples of the substituent having a positive value of σm include, for example, a CF ₃ group (σm = 0.43), a CF ₃ CO group (σm = 0.63), and a HC≡C group (σm = 0.21). , CH ₂ ＣＨCH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH ＝ CH group (σm = 0.21), PhCO group (σm = 0.34), H ₂ NCOCH ₂ group (σm = 0.06) and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

In the present invention, EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
In the formula, R ^{x1 to} R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aryl group.

In the present invention, the carboxylate anion is also preferably represented by the following formula (X).
In the formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, —NR ^X — and a combination thereof, and R ^X represents a hydrogen atom, Represents an alkyl group, an alkenyl group or an aryl group.

  Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion. These can be preferably used.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-6).

In the above general formula, R ¹⁰¹ represents an n-valent organic group,
R ^{102 to} R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group,
R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group;
R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring;
Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group,
n represents an integer of 1 or more;
m represents an integer of 0 to 5.

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring. Examples of the ring include an aliphatic ring (a non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. The ring may be monocyclic or polycyclic. Examples of the linking group in the case where the above groups are bonded to form a ring include a group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aryl group, and a combination thereof. The divalent linking group selected is mentioned. Specific examples of the ring formed include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole Ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring and the like.

In the present invention, the ammonium cation preferably has a structure represented by the formula (Y1-1) or (Y1-2), is represented by the formula (Y1-1) or the formula (Y1-2), and R ¹⁰¹ is aryl. The structure which is a group is more preferable, and the structure represented by the formula (Y1-1) and R ¹⁰¹ is an aryl group is particularly preferable. That is, in the present invention, the ammonium cation is more preferably represented by the following formula (Y).
In the formula (Y), Ar ¹⁰ represents an aromatic group, R ^{11 to} R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁴ and R ¹⁵ are bonded to each other to form a ring. And n represents an integer of 1 or more.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is not particularly limited, but is preferably an alkyl group, an alkenyl group, or an aryl group.
R ¹¹ and R ¹² are preferably a hydrogen atom.

R ^{13 to} R ¹⁵ represent a hydrogen atom or a hydrocarbon group.
Examples of the hydrocarbon group include the hydrocarbon groups described above for R ¹¹ and R ¹² . R ^{13 to} R ¹⁵ are particularly preferably an alkyl group, and preferred embodiments are also the same as those described for R ¹¹ and R ¹² .

R ¹⁴ and R ¹⁵ may combine with each other to form a ring. Examples of the ring include a cyclic aliphatic (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. The ring may be monocyclic or polycyclic. When R ¹⁴ and R ¹⁵ are combined to form a ring, the linking group includes —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and a combination thereof. And a divalent linking group selected from the group consisting of: Specific examples of the ring formed include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole Ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring and the like.

R ^{13 to} R ¹⁵ may be such that R ¹⁴ and R ¹⁵ are bonded to each other to form a ring, or R ¹³ is a linear alkyl group having 5 to 30 carbon atoms (more preferably 6 to 18 carbon atoms). It is preferred that R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms). According to this aspect, it is possible to easily generate an amine species having a high boiling point.
Further, from the viewpoint of the basicity and boiling point of the generated amine species, the total number of carbon atoms of R ¹³ , R ^14, and R ¹⁵ is preferably 7 to 30, and more preferably 10 to 20.
In addition, from the viewpoint that amine species having a high boiling point are easily generated, the chemical formula amount of “—NR ¹³ R ¹⁴ R ¹⁵ ” in the formula (Y) is preferably from 80 to 2,000, and more preferably from 100 to 500.

As an embodiment for further improving the adhesion to a metal layer such as copper, in the formula (Y), R ¹³ and R ¹⁴ are a methyl group or an ethyl group, and R ¹⁵ is a straight chain having 5 or more carbon atoms. Examples include a chain, branched or cyclic alkyl group or an aryl group. R ¹³ and R ¹⁴ are methyl groups, and R ¹⁵ is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, a cyclic alkyl group having 6 to 10 carbon atoms, or a phenyl group. R ¹³ and R ¹⁴ are methyl groups, and R ¹⁵ is a linear alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, a cyclic alkyl group having 6 to 8 carbon atoms or a phenyl group. Is more preferable. By lowering the hydrophobicity of the amine species in this way, even when the amine adheres to a metal layer such as copper, the affinity between the metal layer and polyimide or the like can be increased.

  In the present invention, the acidic compound is also preferably a compound represented by the following formula (A1). This compound is acidic at room temperature, but by heating, the carboxyl group is decarboxylated or dehydrated and cyclized to be lost, so that the previously neutralized and inactivated amine moiety becomes active, and thus the base is formed. And sex. Hereinafter, equation (A1) will be described.

Formula (A1)
In the formula (A1), A ¹ represents a p-valent organic group, R ¹ represents a monovalent organic group, L ¹ represents a (m + 1) -valent linking group, m represents an integer of 1 or more; p represents an integer of 1 or more.

In the formula (A1), A ¹ represents a p-valent organic group. Examples of the organic group include an aliphatic group and an aromatic group, and an aromatic group is preferable. When A ¹ is an aromatic group, a base having a higher boiling point can be easily generated at a lower temperature. By increasing the boiling point of the generated base, volatilization or decomposition due to heating during curing of the polyimide precursor can be suppressed, and cyclization of the polyimide precursor can be more effectively advanced.
Examples of the monovalent aliphatic group include an alkyl group and an alkenyl group.
1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, 1-10 are still more preferable. The alkyl group may be linear, branched or cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, and the like.
The carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10. The alkenyl group may be linear, branched or cyclic. The alkenyl group may have a substituent or may be unsubstituted. Examples of the alkenyl group include a vinyl group and a (meth) allyl group.
Examples of the divalent or higher valent aliphatic group include groups obtained by removing one or more hydrogen atoms from the above monovalent aliphatic group.
The aromatic group may be monocyclic or polycyclic. The aromatic group may be an aromatic heterocyclic group containing a hetero atom. The aromatic group may have a substituent or may be unsubstituted. Unsubstituted is preferred. Specific examples of the aromatic group include a benzene ring group, a naphthalene ring group, a pentalene ring group, an indene ring group, an azulene ring group, a heptalene ring group, an indacene ring group, a perylene ring group, a pentacene ring group, an acenaphthene ring group and a phenanthrene ring. Ring group, anthracene ring group, naphthacene ring group, chrysene ring group, triphenylene ring group, fluorene ring group, biphenyl ring group, pyrrole ring group, furan ring group, thiophene ring group, imidazole ring group, oxazole ring group, thiazole ring group , Pyridine ring group, pyrazine ring group, pyrimidine ring group, pyridazine ring group, indolizine ring group, indole ring group, benzofuran ring group, benzothiophene ring group, isobenzofuran ring group, quinolidine ring group, quinoline ring group, phthalazine ring Group, naphthyridine ring group, quinoxaline ring group, quinoxazoline ring group, isoquinoline ring A carbazole ring group, a phenanthridine ring group, an acridine ring group, a phenanthroline ring group, a thiantrene ring group, a chromene ring group, a xanthene ring group, a phenoxatiin ring group, a phenothiazine ring group, and a phenazine ring group. Most preferred is a benzene ring group.
In the aromatic group, a plurality of aromatic rings may be linked via a single bond or a linking group described below. As the linking group, for example, an alkylene group is preferable. The alkylene group is preferably straight-chain or branched. Specific examples of the group in which a plurality of aromatic rings are linked via a single bond or a linking group include a biphenyl group, a diphenylmethane group, a diphenylpropane group, a diphenylisopropane group, a triphenylmethane group, and a tetraphenylmethane group. .

Examples of the substituent which the organic group represented by A ¹ may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methoxy group, an ethoxy group and a tert-butoxy group. Aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group; acetoxy group, propionyloxy group and benzoyloxy group Acyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; acyl group; methylsulfanyl group and tert-butylsulfanyl group; alkylsulfanyl group; phenylsulfanyl And arylsulfanyl groups such as p-tolylsulfanyl group; alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; halogenated alkyl groups such as alkyl fluoride group; cyclopentyl group, cyclohexyl group and cycloheptyl Groups and cycloalkyl groups such as adamantyl group; aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxyl group; carboxyl group; formyl group; sulfo group; Alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; diarylamino group; thioxy group; or a combination thereof.

L ¹ represents a (m + 1) -valent linking group. Is not particularly restricted but includes linking group, -COO -, - OCO -, - CO -, - O -, - S -, - SO -, - SO 2 -, an alkylene group (preferably a linear 1 to 10 carbon atoms A chain or branched alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 10 carbon atoms), an alkenylene group (preferably a linear or branched alkenylene group having 210 carbon atoms), or a linking group in which a plurality of these are linked And the like. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group, or an alkenylene group, more preferably a linear or branched alkylene group, further preferably a linear alkylene group, particularly preferably an ethylene group or a methylene group, and most preferably a methylene group.

R ¹ represents a monovalent organic group. Examples of the monovalent organic group include an aliphatic group and an aromatic group. Aliphatic group, for aromatic groups include those described in A ¹ described above. The monovalent organic group represented by R ¹ may have a substituent. Examples of the substituent include those described above.
R ¹ is preferably a group having a carboxyl group. That is, R ¹ is preferably a group represented by the following formula.
-L ² - _{(COOH) n}
Wherein, ^{L 2} represents a (n + 1) valent connecting group, n represents an integer of 1 or more.
Linking group L ² represent it may include the groups described by L ¹ described above, and preferred ranges are also the same, particularly preferably an ethylene group or a methylene group, a methylene group is most preferred.
n represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of n is the maximum number of substituents that can take the linking group L ² represents. If n is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C. or lower. Further, the stability of the resin composition can be improved.

m represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of m is the maximum number of substituents that the linking group represented by L ¹ can have. When m is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C. or lower. Further, the stability of the resin composition can be improved.
p represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of p is the maximum number of substituents that can take the organic group A ¹ represents. When p is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C. or lower.

In the present invention, the compound represented by the formula (A1) is preferably a compound represented by the following formula (1a).
In the formula (1a), A ¹ represents a p-valent organic group, L ¹ represents a (m + 1) -valent connecting group, L ² represents a (n + 1) -valent connecting group, and m represents an integer of 1 or more. Represents, n represents an integer of 1 or more, and p represents an integer of 1 or more.
A ¹ , L ¹ , L ² , m, n and p in the general formula (1a) have the same meanings as the ranges described in the general formula (A1), and the preferred ranges are also the same.

In the present invention, the compound represented by the formula (A1) is preferably N-aryliminodiacetic acid. In N-aryliminodiacetic acid, A ¹ in the general formula (A1) is an aromatic group, L ¹ and L ² are methylene groups, m is 1, n is 1, and p is 1. A certain compound. N-aryliminodiacetic acid easily generates a tertiary amine having a high boiling point at 120 to 200 ° C.

  Hereinafter, specific examples of the thermal base generator will be described, but the present invention is not limited thereto. These can be used alone or in combination of two or more. Me in the following formula represents a methyl group. Among the compounds shown below, (A-1) to (A-11), (A-18) and (A-19) are compounds represented by the above formula (A1). Among the compounds shown below, (A-1) to (A-11), (A-18) to (A-26) are more preferable, and (A-1) to (A-9), (A-18) ) To (A-21), (A-23) and (A-24) are more preferred.

  As the thermal base generator used in the present invention, the compounds described in Paragraph Nos. 0015 to 0055 of Japanese Patent Application No. 2015-034388 are also preferably used, and the contents thereof are incorporated herein.

When a thermal base generator is used, the content of the thermal base generator in the resin composition is preferably from 0.1 to 50% by mass based on the total solid content of the resin composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
One or two or more thermal base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

<< thermal radical polymerization initiator >>
The resin composition in the present invention may contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. A thermal radical polymerization initiator is a compound that generates a radical by the energy of heat and initiates or promotes a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the polyimide precursor is advanced. Further, when the polyimide precursor contains a radical polymerizable group, the polymerization reaction of the polyimide precursor can be advanced together with the cyclization of the polyimide precursor, so that higher heat resistance can be achieved.
Examples of the thermal radical polymerization initiator include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borates, azinium compounds, metallocene compounds, active ester compounds, and carbon halides. Compounds having a bond, azo compounds and the like can be mentioned. Among them, peroxides and azo compounds are more preferable, and peroxides are particularly preferable.
The 10-hour half-life temperature of the thermal radical polymerization initiator used in the present invention is preferably 90 to 130 ° C, more preferably 100 to 120 ° C.
Specific examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
As commercial products, Perbutyl Z and Park Mill D (manufactured by NOF Corporation) can be suitably used.

  When the resin composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably from 0.1 to 50% by mass, and more preferably from 0.1 to 30% by mass based on the total solid content of the resin composition. Is more preferable, and 0.1 to 20% by mass is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance. The thermal radical polymerization initiator may be only one kind or two or more kinds. When two or more thermal radical polymerization initiators are used, the total is preferably within the above range.

<<< rust inhibitor >>>
The resin composition of the present invention preferably contains a rust inhibitor. When the resin composition contains the rust inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the resin composition layer. Examples of the rust preventive include rust preventives described in paragraph 0094 of JP-A-2013-15701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and paragraph 0052 of JP-A-2011-59656. And the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520 and the like can be used. Specifically, heterocycles (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 Having a ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring and a 6H-pyran ring, a triazine ring), a compound having a thiourea or a mercapto group, a hindered phenol compound, a salicylic acid derivative compound, and hydrazide. Derivative compounds are mentioned. Among them, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole are preferred, and 1,2,4-triazole, 1,2,3-benzotriazole and 5-methyl-1H-benzotriazole are preferred. 1,1H-tetrazole, 5-methyl-1H-tetrazole and 5-phenyl-1H-tetrazole are more preferred, and 1H-tetrazole is most preferred. Commercially available products include KEMITEC BT-C (1,2,3-benzotriazole, manufactured by Chemipro Kasei), 1HT (manufactured by Toyobo, 1H-tetrazole), P5T (manufactured by Toyobo, 5- Phenyl-1H-tetrazole) and the like.

  When the resin composition contains a rust inhibitor, the content of the rust inhibitor is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the resin. Only one type of rust inhibitor may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.

<< Silane coupling agent >>
The resin composition in the present invention preferably contains a silane coupling agent for improving the adhesiveness to a metal material used for an electrode, a wiring, or the like. Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO2011 / 080992A1, and JP-A-2014-191252. The compounds described in paragraphs 0060 to 0061, the compounds described in paragraphs 0045 to 0052 of JP-A-2014-41264, and the compounds described in paragraph 0055 of International Publication WO2014 / 099754. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. It is also preferable to use 2-((3- (triethoxysilyl) propyl) carbamoyl) benzoic acid, triethoxysilylpropylmaleamic acid, or the following compound as the silane coupling agent. In the following formula, Et represents an ethyl group. As a commercially available product, KBM-602 (N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used.

  The silane coupling agent is preferably used in an amount of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the resin. When the content of the silane coupling agent is 0.1 parts by mass or more, the adhesion of the obtained film to the metal layer becomes good, and the content of the silane coupling agent is 30 parts by mass or less. The heat resistance and mechanical properties of the film are improved. The silane coupling agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably within the above range.

<< Solvent >>
In the present invention, when the resin composition is formed into a layer by coating, it is preferable to add a solvent to the resin composition. As the solvent, any known solvent can be used. For example, compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and the like can be mentioned.
As esters, for example, ethyl acetate, n-butyl acetate, isobutyl 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 (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butylalkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, methyl ethoxyacetate, etc.) )), Alkyl 3-alkyloxypropionates (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate) Ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), alkyl 2-alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2- Propyl alkyloxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy Methyl-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Pyruvate Le, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-ethyl-oxobutanoate can be preferably used.
As ethers, for example, 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, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like.
As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferably mentioned.
Dimethyl sulfoxide and the like are preferred as the sulfoxides.

  From the viewpoint of improving the properties of the coated surface, a form in which two or more solvents are mixed is also preferable. Among them, 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, propylene glycol methyl ether, and a mixed solution composed of two or more selected from propylene glycol methyl ether acetate. Particularly preferred is a combination of dimethyl sulfoxide and γ-butyrolactone.

When the resin composition has a solvent, the content of the solvent is preferably set to an amount such that the total solid content of the resin composition becomes 5 to 80% by mass, and from 5 to 70% by mass, from the viewpoint of applicability. Further preferred is 10 to 60% by mass. The solvent content may be adjusted according to the desired thickness and the coating method. For example, when the coating method is spin coating or slit coating, the content of the solvent having a solid content concentration in the above range is preferable. In the case of spray coating, the amount is preferably 0.1% to 50% by mass, more preferably 1.0% to 25% by mass. By adjusting the amount of the solvent by the coating method, a resin composition layer having a desired thickness can be formed uniformly.
The solvent may be only one kind or two or more kinds. When two or more solvents are used, the total is preferably within the above range.
Further, the content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide is determined based on the total weight of the resin composition from the viewpoint of film strength. And preferably less than 1% by mass, more preferably less than 0.5% by mass, and even more preferably less than 0.1% by mass.

<< Sensitizing dye >>
The resin composition in the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific actinic radiation and enters an electronically excited state. The sensitizing dye in the electronically excited state comes into contact with a thermal base generator, a photobase generator, a thermal radical polymerization initiator, a photopolymerization initiator, or the like, and causes effects such as electron transfer, energy transfer, and heat generation. Thus, the thermal base generator, the photobase generator, the thermal radical polymerization initiator, and the photopolymerization initiator undergo a chemical change and are decomposed to generate radicals, acids, or bases. For details of the sensitizing dye, the description of paragraphs 0161 to 0163 of JP-A-2006-027357 can be referred to, and the contents are incorporated in the present specification. When the resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. 0.5 to 10% by mass is more preferable. The sensitizing dyes may be used alone or in combination of two or more.

<< Chain transfer agent >>
The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary, Third Edition (edited by The Society of Polymer Science, 2005), pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These can generate a radical by donating hydrogen to a low-activity radical species, or can generate a radical by being oxidized and then deprotonated. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole, etc.) can be preferably used. When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total solid content of the resin composition. Parts, more preferably 1 to 5 parts by mass. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably within the above range.

<< Surfactant >>
Various surfactants may be added to the resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Further, the following surfactants are also preferable.

  When the resin composition contains a surfactant, the content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 2.0% by mass, based on the total solid content of the resin composition. 1.0% by mass. The surfactant may be only one kind or two or more kinds. When two or more surfactants are contained, the total is preferably within the above range.

<< 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 is added to the resin composition of the present invention, and the composition is dried on the surface of the composition during application. It may be unevenly distributed. When the resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition. The higher fatty acid derivative may be only one kind or two or more kinds. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.

<< other additives >>
The resin composition of the present invention is, as long as the effects of the present invention are not impaired, various additives, for example, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, and an agglomerate. An inhibitor and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition.

<<<< Restrictions on other contained substances >>>>
The water content of the resin composition in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the properties of the coated surface.

The metal content of the resin composition in the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass from the viewpoint of insulating properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably within the above range.
Further, as a method for reducing metal impurities unintentionally contained in the resin composition, a material having a low metal content is selected as a material constituting the resin composition, and a filter is applied to the material constituting the resin composition. Examples of the method include filtration, and distillation under the condition that contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

  In the resin composition of the present invention, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosion. Above all, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine and bromine atoms or the sum of chloride and bromide ions is within the above range.

<Preparation of resin composition>
The resin composition can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the resin composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore sizes and / or materials may be used in combination. Further, various materials may be filtered plural times. When filtration is performed a plurality of times, circulation filtration may be used. Also, filtration may be performed under pressure. In the case of performing filtration by applying pressure, the pressure to be applied is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to the filtration using a filter, an impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Electronic device>
Next, an embodiment of an electronic device obtained by applying the method for manufacturing a laminate of the present invention will be described. The electronic device 100 shown in FIG. 2 is a so-called three-dimensional mounting device, in which a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120. In this embodiment, the case where the number of stacked semiconductor elements (semiconductor chips) is four is mainly described, but the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. Layers, eight layers, sixteen layers, thirty-two layers, or the like. Further, it may be a single layer.

Each of the plurality of semiconductor elements 101a to 101d is formed of a semiconductor wafer such as a silicon substrate.
The uppermost semiconductor element 101a has no through electrode, and has an electrode pad (not shown) formed on one surface thereof.
The semiconductor elements 101b to 101d have penetrating electrodes 102b to 102d, and connection pads (not shown) provided integrally with the penetrating electrodes are provided on both surfaces of each semiconductor element.

The stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and a semiconductor element 101b to 101d having through electrodes 102b to 102d are flip-chip connected.
That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the through electrode 102b adjacent thereto are connected by a metal bump 103a such as a solder bump. A connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to a connection pad on the semiconductor element 101b side of the semiconductor element 101c having the through electrode 102c adjacent thereto by a metal bump 103b such as a solder bump. Similarly, the connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the through electrode 102d adjacent thereto by a metal bump 103c such as a solder bump. ing.

  An underfill layer 110 is formed in a gap between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.

The laminate 101 is laminated on the wiring board 120.
As the wiring board 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used. Examples of the wiring board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).

On one surface of the wiring board 120, a surface electrode 120a is provided.
An insulating layer 115 on which the rewiring layer 105 is formed is disposed between the wiring board 120 and the laminate 101, and the wiring board 120 and the laminate 101 are electrically connected via the rewiring layer 105. It is connected. The insulating layer 115 is formed by using the method for manufacturing a laminate of the present invention. The insulating layer 115 may be a laminate having a multilayer wiring structure as shown in FIG.
One end of the rewiring layer 105 is connected to an electrode pad formed on a surface of the semiconductor element 101d on the rewiring layer 105 side via a metal bump 103d such as a solder bump. The other end of the rewiring layer 105 is connected to a surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
An underfill layer 110a is formed between the insulating layer 115 and the stacked body 101. An underfill layer 110b is formed between the insulating layer 115 and the wiring board 120.

<Electronic device manufacturing method>
Next, a method for manufacturing an electronic device of the present invention will be described. The method for manufacturing an electronic device of the present invention includes the above-described method for manufacturing a laminate of the present invention. In the method of manufacturing an electronic device according to the present invention, it is preferable to manufacture a plurality of electronic devices under the same storage step conditions.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples as long as the gist is not exceeded. Unless otherwise specified, “%” and “parts” are based on mass. NMR is an abbreviation for nuclear magnetic resonance.

(Synthesis example 1)
[Synthesis of polyimide precursor (P-1: polyimide precursor having no radical polymerizable group) from pyromellitic dianhydride, 4,4'-oxydianiline and benzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol are suspended in 50 ml of N-methylpyrrolidone. And dried over molecular sieves. The suspension was heated at 100 ° C. for 3 hours. A few minutes after starting the heating, a clear solution was obtained. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 ml of N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) SOCl ₂ was added over 10 minutes keeping the temperature at −10 ± 4 ° C. While adding SOCl _2, viscosity is increased. After dilution with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 mmol) of 4,4′-oxydianiline dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at a speed of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added again to 4 liters of water, stirred for another 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain a polyimide precursor (P-1) containing a repeating unit represented by the following formula.

(Synthesis example 2)
[Synthesis of a polyimide precursor (P-2: a polyimide precursor having a radical polymerizable group) from pyromellitic dianhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10 g 0.7 g of pyridine and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester is chlorinated with SOCl ₂ and then converted to a polyimide precursor with 4,4′-oxydianiline in the same manner as in Synthesis Example 1. The polyimide precursor (P-2) containing the repeating unit represented by these was obtained.

(Synthesis example 3)
[Synthesis of polyimide precursor (P-3: polyimide precursor having a radical polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) of 4,4′-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate and 0.05 g of hydroquinone And 10.7 g of pyridine and 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester is chlorinated with SOCl ₂ and then converted to a polyimide precursor with 4,4′-oxydianiline in the same manner as in Synthesis Example 1. The polyimide precursor (P-3) containing the repeating unit represented by these was obtained.

(Synthesis Example 4) [Synthesis of acrylic polymer (P-6)]
27.0 g (153.2 mmol) of benzyl methacrylate, 20 g (157.3 mmol) of N-isopropyl methacrylamide, 39 g (309.2 mmol) of allyl methacrylate, 13 g (151.0 mmol) of methacrylic acid, 3.55 g (15.4 mmol) of a polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries) and 300 g of 3-methoxy-2-propanol were mixed. The mixture was dropped into 300 g of 3-methoxy-2-propanol heated to 75 ° C over 2 hours under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was further stirred at 75 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was poured into 5 liters of water to precipitate the polymer, and the mixture was stirred at a speed of 5000 rpm for 15 minutes. The acrylic resin was collected by filtration, poured again into 4 liters of water, stirred for 30 minutes, and filtered again. Next, the obtained acrylic resin was dried at 45 ° C. for 3 days under reduced pressure to obtain an acrylic polymer (P-6) represented by the following formula.

<Preparation of photosensitive resin composition>
The components described below were mixed to prepare a coating solution of the photosensitive resin composition as a uniform solution.
(composition)
Resin: parts by mass in the following table Radical polymerizable compound: parts by mass in the following table Photo-radical polymerization initiator: parts by mass in the following table Silane coupling agent: parts by mass in the following table Rust inhibitor: Parts by mass shown in the following table Polymerization inhibitor: parts by mass shown in the following table Base generator: parts by mass shown in the following table Solvent 1 (dimethylsulfoxide): 100 parts by mass Solvent 2 (γ-butyrolactone): 25 parts by mass

Abbreviations described in the table are as follows.
(resin)
P-1 to P-3: polyimide precursors (P-1) to (P-3) synthesized in Synthesis Examples 1 to 3.
P-5: Matrimid 5218 (Huntsman Corporation, ring-closing polyimide)
P-6: acrylic polymer (P-6) synthesized in Synthesis Example 5 (acrylic resin)
P-7: Polymethyl methacrylate (Mw = 15000, manufactured by Sigma-Aldrich Japan GK)

(Radical polymerizable compound)
B-1: SR209 (manufactured by Sartomer, tetraethylene glycol diacrylate)
B-2: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate)
B-3: A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
B-4: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate)

(Photo-radical polymerization initiator)
C-1: IRGACURE OXE 01 (oxime compound, manufactured by BASF)
C-2: IRGACURE OXE 02 (oxime compound manufactured by BASF)
C-3: IRGACURE-784 (manufactured by BASF, metallocene compound)
C-4: ADEKA ARKULS NCI-831 (oxime compound manufactured by ADEKA Corporation)

(Silane coupling agent)
D-1: KBM-602 (Shin-Etsu Chemical Co., Ltd., silane compound having an amino group)
D-2: 2-((3- (triethoxysilyl) propyl) carbamoyl) benzoic acid (manufactured by Aquila Pharmatech LLC, a silane compound having a carboxyl group)
D-3: triethoxysilylpropylmaleamic acid (manufactured by Gelest, Inc., a silane compound having a carboxyl group)

(anti-rust)
E-1: KEMITEC BT-C (1,2,3-benzotriazole, manufactured by Chemipro Kasei Co., Ltd.)
E-2: 1HT (manufactured by Toyobo Co., Ltd., 1H-tetrazole)
E-3: P5T (manufactured by Toyobo Co., Ltd., 5-phenyl-1H-tetrazole)

(Polymerization inhibitor)
F-1: 4-methoxyphenol F-2: p-benzoquinone F-3: 1-nitroso-2-naphthol

(Base generator)
A-1, A-21, A-40: Compound having the following structure (thermal base generator)
A-43: WPBG-266 (a photobase generator manufactured by Wako Pure Chemical Industries, Ltd. This compound is also a compound that decomposes by heating to generate a base, that is, a thermal base generator).

<Manufacture of laminate>
Each photosensitive resin composition was pressure-filtered through a filter having a pore width of 0.8 μm, applied in layers on a silicon wafer by a spin coating method, and dried at 100 ° C. for 5 minutes using a hot plate. Thus, a photosensitive resin composition layer was formed. Next, after performing a storage step (PCD step) at the time and temperature described in the following table, the photosensitive resin composition layer was exposed to light of 500 mJ / cm ² using a stepper (Nikon NSR 2005 i9C). Exposure with energy. Next, the photosensitive resin composition layer after exposure was subjected to a preservation step (PED step) at the time and temperature shown in the following table, and then developed with cyclopentanone for 60 seconds to form a hole having a diameter of 10 μm. Was formed. Next, after performing a storage step (PDD step) at the time and temperature described in the following table, the resin layer (pattern) was formed by heating at 230 ° C. for 3 hours in a nitrogen atmosphere. Next, the resin layer (pattern) after heating is cooled to room temperature, a storage step (PBD step) is performed at a time and a temperature shown in the following table, and then a copper plating process is performed. A laminate 1 was formed by forming a 5 μm copper thin film.
In addition, each preservation | save process was performed by leaving still in the clean thermo-hygrostat (Espec Co., Ltd. product, PCR-3J) adjusted to the setting temperature of the following table | surface.
Next, after irradiating the copper thin film of the laminate 1 with oxygen plasma, the photosensitive resin composition is again applied, exposed, developed, heated and stored, and then subjected to copper plating, A copper thin film having a thickness of 5 μm was formed on the layer to obtain a laminate 2.
Next, after irradiating the copper thin film of the laminate 2 with oxygen plasma, the photosensitive resin composition is again applied, exposed, developed, heated and stored, and then subjected to copper plating. A copper thin film having a thickness of 5 μm was formed on the layer to obtain a laminate 3.

  The storage time under each condition described in the above table is the elapsed time from when the surface temperature reached the set temperature. The fluctuation range of the surface temperature in each storage step was 5 ° C. or less. The average surface temperature in each storage step was almost the same as the set temperature.

<Evaluation>
[Peeling defect (Evaluation 1)]
The laminate 2 was cut in the vertical direction, and a cross section having a width of 5 mm was observed to check whether or not the resin layer / resin layer and the copper / resin layer were peeled off. If there is no peeling, it means that it has excellent adhesion, which is a preferable result.
A: No peeling occurred B: 1 to 2 peeling C: 3 to 5 peeling D: 6 or more peeling

[Peeling defect (Evaluation 2)]
The laminate 3 was cut in the vertical direction, and a cross section having a width of 5 mm was observed to confirm the presence or absence of peeling between the resin layer / resin layer and the copper / resin layer. If there is no peeling, it means that it has excellent adhesion, which is a preferable result.
A: No peeling occurred B: 1 to 2 peeling C: 3 to 5 peeling D: 6 or more peeling

[Limited resolution (Evaluation 3)]
The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR2005 i9C). Exposure was performed using i-line, and exposure was performed at a wavelength of 365 nm using a photomask of a fuse box in increments of 1 μm from 5 μm to 25 μm at each exposure energy of 200 mJ / cm ² . The exposed photosensitive resin composition layer was developed using cyclopentanone and propylene glycol methyl ether acetate as a developing solution. Specifically, the exposed photosensitive resin composition layer was sprayed with cyclopentanone, then sprayed with propylene glycol methyl ether acetate, and developed for 60 seconds. The line width at which the silicon wafer was exposed at the bottom of the fuse box was evaluated according to the following criteria. The smaller the line width, the smaller the width of the metal wiring formed in the subsequent plating step. This is a preferable result. The measurement limit is 5 μm. The results are shown in the table.
A: 5 μm or more and 8 μm or less B: More than 8 μm and 10 μm or less C: More than 10 μm and 15 μm or less D: More than 15 μm

  As shown in the above table, in the example in which the preservation step was performed, a laminate having good adhesion could be manufactured. In addition, the photosensitive resin compositions of Compositions 1 to 12 using a polyimide precursor as a resin have a high limit resolution, and the laminates of Examples 1 to 33, 36, and 37 using this photosensitive resin composition are: In addition, the metal wiring width can be made finer.

100: Electronic devices 101a to 101d: Semiconductor element 101: Stacks 102b to 102d: Through electrodes 103a to 103e: Metal bumps 105: Rewiring layers 110, 110a, 110b: Underfill layer 115: Insulating layer 120: Wiring board 120a: Surface electrodes 201 to 204: resin layers 301 to 303: metal layers 401 to 403: grooves 500: laminate

Claims (15)

Polyimide precursor, polyimide, a resin selected from polybenzoxazole precursor and polybenzoxazole, and a photopolymerization initiator, a photosensitive resin composition containing a photosensitive resin composition layer on a support, the photosensitive resin composition layer Forming a photosensitive resin composition layer forming step,
An exposure step of exposing the photosensitive resin composition layer to a pattern,
A developing step of developing the photosensitive resin composition layer to form a pattern,
A heating step of heating the pattern,
Metal layer forming step of forming a metal layer on the pattern after heating,
Between the photosensitive resin composition layer forming step and the exposing step, between the exposing step and the developing step, between the developing step and the heating step, and at least one between the heating step and the metal layer forming step Performing a storage step of storing the surface temperature for at least 5 minutes after the surface temperature reaches a certain temperature, wherein the storage is performed between the photosensitive resin composition layer forming step and the exposing step. A method of manufacturing a laminate for performing the steps .   The method for producing a laminate according to claim 1, wherein the storage step is performed between an exposure step and a development step. The method for producing a laminate according to claim 2, wherein the storage step performed between the exposure step and the development step satisfies the following formula;
5 ≦ t1 <( ^{10−0.036 × T1 + 12.3} ) × 60
T1 is the average surface temperature in the storage step performed between the exposure step and the development step, and is expressed in K; t1 is the time of the storage step performed between the exposure step and the development step, in minutes. is there. The method for producing a laminate according to any one of claims 1 to 3 , wherein the storage step performed between the photosensitive resin composition layer forming step and the exposure step satisfies the following formula;
5 ≦ t2 <( ^{10−0.031 × T2 + 10.7} ) × 60
T2 is the average surface temperature in the storage step performed between the photosensitive resin composition layer forming step and the exposing step, and the unit is K; t2 is between the photosensitive resin composition layer forming step and the exposing step. The time of the preservation step to be performed, the unit being minutes. Performing the storing step between the developing step and the heating step, method for producing a laminate according to any one of claims 1 to 4. The method for producing a laminate according to claim 5, wherein the storing step performed between the developing step and the heating step satisfies the following formula;
5 ≦ t3 <( ^{10−0.02 × T3 + 8.0} ) × 60
T3 is the average surface temperature in the storage step performed between the development step and the heating step, and is expressed in K; t3 is the time of the storage step performed between the development step and the heating step, in minutes. is there. Performing the storing step between the heating step and the metal layer forming step, method for producing a laminate according to any one of claims 1 to 6. The resin in the photosensitive resin composition is a polyimide precursor,
The laminate according to any one of claims 1 to 7 , wherein the polyimide precursor contains a radical polymerizable group, or the photosensitive resin composition contains a radical polymerizable compound other than the polyimide precursor. Manufacturing method. The method for producing a laminate according to any one of claims 1 to 8 , wherein the polyimide precursor includes a repeating unit represented by the following formula (1);
Equation (1)
In the formula (1), A ²¹ and A ²² each independently represent an oxygen atom or —NH—, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group. In the formula (1), at least one of R ²³ and R ²⁴ comprises a radical polymerizable group, method for producing a laminate according to claim 9. The method according to claim 9 , wherein R ²² in the formula (1) is a tetravalent group containing an aromatic ring. On the pattern after the metal layer forming step, the photosensitive resin composition layer forming step, the exposing step, the developing step, the heating step and the metal layer forming step are performed in this order, and the photosensitive resin composition At least one of a step between a layer forming step and the exposing step, a step between the exposing step and the developing step, a step between the developing step and the heating step, and a step between the heating step and the metal layer forming step. in one, said storing step performs two cycles or more series of cycles to perform, method for producing a laminate according to any one of claims 1 to 11. The method for producing a laminate according to any one of claims 1 to 12 , which is a method for producing a laminate having a multilayer wiring structure. Polyimide precursor, polyimide, a resin selected from polybenzoxazole precursor and polybenzoxazole, and a photopolymerization initiator, a photosensitive resin composition containing a photosensitive resin composition layer on a support, the photosensitive resin composition layer Forming a photosensitive resin composition layer forming step,
An exposure step of exposing the photosensitive resin composition layer to a pattern,
A developing step of developing the photosensitive resin composition layer to form a pattern,
A heating step of heating the pattern,
Metal layer forming step of forming a metal layer on the pattern after heating,
Between the photosensitive resin composition layer forming step and the exposing step, between the exposing step and the developing step, between the developing step and the heating step, and at least one between the heating step and the metal layer forming step Performing a storage step of storing the surface temperature for at least 5 minutes after the surface temperature reaches a certain temperature, wherein the storage is performed between the photosensitive resin composition layer forming step and the exposing step. A method for manufacturing an electronic device, including a method for manufacturing a laminate that performs a step . The method of manufacturing an electronic device according to claim 14, wherein a plurality of electronic devices are manufactured under the same storage process conditions.