JP2017129768A - Photosensitive resin composition, method for producing cured product, cured film, display device, and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is excellent in developability and from which a cured product excellent in hardness and corrosion-preventing properties to metal wiring is obtained, a method for producing a cured product using the photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and a display device and a touch panel using the cured film.SOLUTION: The photosensitive resin composition contains: a specific polymer component; a quinonediazide compound; a solvent; at least one heterocyclic compound selected from the group consisting of a triazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, and a benzimidazole compound; and a maleimide compound.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a method for producing a cured product, a cured film, a display device, and a touch panel.

Flat panel displays such as liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used. In recent years, capacitive touch panels have attracted attention with the spread of smartphones and tablet terminals. The sensor substrate of the capacitive touch panel has a transparent electrode (ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) etc.) and a metal electrode (silver, copper, molybdenum, titanium, aluminum, etc.) on glass or film, and Such a laminated body and an alloy thereof have a patterned wiring, and in addition, a structure having a protective film for protecting an insulating film, ITO, and metal at a crossing portion of the wiring is general.
As a conventional photosensitive resin composition, what was described in patent document 1 is known.

JP 2013-152353 A

  The problem to be solved by the present invention is a photosensitive resin composition excellent in developability, hardness of the resulting cured product and excellent corrosion resistance to metal wiring, and curing using the photosensitive resin composition It is providing the manufacturing method of a thing, the cured film formed by hardening | curing the said photosensitive resin composition, and the display apparatus and touch panel using the said cured film.

The above-described problems of the present invention have been solved by means described in the following <1>, <10>, <12> or <14>. It is described below together with <2> to <9>, <11> and <13> which are preferred embodiments.
<1> A polymer component satisfying at least one of the following I and II, a quinonediazide compound, a solvent, a triazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, and a benzimidazole compound A photosensitive resin composition comprising at least one heterocyclic compound and a maleimide compound,
I: a polymer component containing a polymer having a structural unit having a carboxy group and / or a salt thereof, and a structural unit having an epoxy group and / or an oxetanyl group II: a structural unit having a carboxy group and / or a salt thereof And a polymer component comprising a polymer having a structural unit having an epoxy group and / or an oxetanyl group <2> The heterocyclic compound is a compound represented by any one of the following formulas D1 to D12 The photosensitive resin composition according to <1>,

In Formula D1 to Formula D12, R ¹ , R ⁵ , R ⁷ , R ⁹ , R ²⁰ and R ²⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or an amino group, and R ² to R ⁴ , R ⁸ , R ^{10 to} R ¹³ , R ^{15 to} R ¹⁸ , R ²² , R ²⁴ and R ^{26 to} R ²⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, Represents an alkylamino group, an arylamino group, a mercapto group, an alkylthio group or an arylthio group, and R ⁶ , R ¹⁴ , R ²¹ and R ²³ each independently represent a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group; , Alkylamino group, arylamino group, mercapto group, alkylthio group, arylthio group, carboxy group, hydroxy group, alkoxy group or It represents an aryloxy ^{group, R 19} represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n1 to n4 each independently represent an integer of 0 to 4.

  <3> The photosensitive resin composition according to <1> or <2>, wherein the maleimide compound includes a compound represented by the following formula E1.

In formula E1, each R ^e1 independently represents a single bond, an alkylene group, —SO ₂ —, —SO—, —S— or —O—, and each R ^e2 independently represents a halogen atom or an alkyl group. , M1 represents an integer of 0 to 5, and m2 independently represents an integer of 0 to 4.

<4> The photosensitive resin composition according to any one of <1> to <3>, further including silica particles,
<5> The photosensitive resin composition according to <4>, wherein an average primary particle size of the silica particles is 1 to 50 nm.
<6> The photosensitive resin composition according to <4> or <5>, wherein the content of the silica particles is 5% by mass or more and less than 40% by mass with respect to the total solid content of the photosensitive resin composition,
<7> The photosensitive resin composition according to <2>, wherein the heterocyclic compound is a compound represented by any one of the formulas D1, D2 and D4 to D12.
<8> The photosensitive resin composition according to <7>, wherein the heterocyclic compound is a compound represented by any one of the formulas D4 to D12.
<9> A method for producing a cured product comprising at least steps a to d in this order,
Step a: Application step of applying the photosensitive resin composition according to any one of <1> to <8> on a substrate Step b: Solvent removal step of removing the solvent from the applied photosensitive resin composition Step c: Exposure step of exposing at least a part of the photosensitive resin composition from which the solvent has been removed with actinic rays Step d: Heat treatment step of heat-treating the exposed photosensitive resin composition <10> Step c and step d A process for producing a cured product according to <9>, including step e,
Step e: Development step of developing the exposed photosensitive resin composition with an aqueous developer <11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <8> ,
<12> The cured film according to <11>, which is an interlayer insulating film or an overcoat film,
<13> A display device having the cured film according to <11> or <12>,
<14> A touch panel having the cured film according to <11> or <12>.

  According to the present invention, a photosensitive resin composition excellent in developability, hardness of the resulting cured product and excellent corrosion resistance to metal wiring, and a method for producing a cured product using the photosensitive resin composition A cured film formed by curing the photosensitive resin composition, and a display device and a touch panel using the cured film can be provided.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. 1 is a conceptual diagram illustrating a configuration of an example of a liquid crystal display device having a touch panel function. FIG. 5 shows a conceptual diagram of a configuration of another example of a liquid crystal display device having a touch panel function.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements 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 present specification, when a numerical range is expressed as “to”, the numerical range means a range including a lower limit value and an upper limit value described before and after the numerical range. The organic EL element in the present invention refers to an organic electroluminescence element.
Regarding the notation of the compounds in the present specification, the notation of “group (atomic group)” with no substitution and no substitution includes groups having a substituent together with the unsubstituted group. 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 addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In the present invention, “a polymer component containing a polymer having a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group” or the like is also simply referred to as “component A” or the like.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
Moreover, in this invention, the combination of 2 or more of a preferable aspect is a more preferable aspect.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention includes a polymer component that satisfies at least one of the following I and II, a quinonediazide compound, a solvent, a triazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, and a benzoate. It contains at least one heterocyclic compound selected from the group consisting of imidazole compounds and a maleimide compound.
I: a polymer component comprising a polymer having a structural unit having a carboxy group and / or a salt thereof, and a structural unit having an epoxy group and / or an oxetanyl group II: a structural unit having a carboxy group and / or a salt thereof Polymer component including polymer having polymer and polymer having constitutional unit having epoxy group and / or oxetanyl group

Although the detailed mechanism of the present invention is unknown, as a result of detailed studies by the present inventors, a specific polymer component, a quinonediazide compound, a solvent, a specific heterocyclic compound, and a maleimide compound are obtained. It has been found that a photosensitive resin composition excellent in developability and excellent in the hardness of the resulting cured product and the corrosion resistance to metal wiring can be obtained by the inclusion.
Hereinafter, each component of the photosensitive resin composition will be described in order.

<Polymer component satisfying at least one of I and II>
The photosensitive resin composition of the present invention contains a polymer component that satisfies at least one of the following I and II.
I: a polymer component containing a polymer having a structural unit having a carboxy group and / or a salt thereof, and a structural unit having an epoxy group and / or an oxetanyl group II: a structural unit having a carboxy group and / or a salt thereof Polymer component including polymer having polymer having polymer having epoxy group and / or oxetanyl group and carboxy group and / or salt thereof, epoxy group and / or oxetanyl as a whole By having a crosslinkable group, a curing reaction is possible.

The polymer component is preferably a polymer component satisfying I.
Moreover, the photosensitive resin composition of this invention may contain polymers other than the polymer shown to said I and II further.

Each polymer in the polymer component is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. Further, “(meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.

-Structural unit having a carboxy group and / or a salt thereof-
The polymer component contains at least a polymer having a structural unit having a carboxy group and / or a salt thereof.
When the polymer component has a carboxy group and / or a salt thereof, the polymer component is easily dissolved in an alkaline developer and not only developability is improved, but also sensitivity is excellent and adhesion after development is also excellent.
The salt of the carboxy group is a group obtained by neutralizing the carboxy group to have a salt structure, and the salt is not particularly limited, but an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and an organic ammonium salt. Preferred examples include salts.
Among these, a structural unit having a carboxy group is preferable.

Specifically, as the structural unit having a carboxy group, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and an ethylenically unsaturated group and a structure derived from an acid anhydride are combined. The structural unit which has is mentioned.
Examples of the unsaturated carboxylic acid used for forming the structural unit having a carboxy group include those listed below.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Examples include hexahydrophthalic acid and 2- (meth) acryloyloxyethyl phthalic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be its acid anhydride. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.

The structural unit having both the ethylenically unsaturated group and the structure derived from an acid anhydride is derived from a monomer obtained by reacting a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride. It is preferable that it is a unit.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, and more preferably 30 to 100 mol%, from the viewpoint of developability.

  Among them, as a structural unit having a carboxy group and / or a salt thereof, a structural unit derived from methacrylic acid (a structural unit represented by the following formula a1-1) or a structural unit derived from acrylic acid (represented by the following formula a1-2). The structural unit is preferably a structural unit derived from methacrylic acid (the structural unit represented by the following formula a1-1).

In formula a1-1 and formula a1-2, R ^a each independently represents a hydrogen atom, an alkali metal cation, an alkaline earth metal cation, an ammonium ion, or an organic ammonium ion.
Among these, Ra is preferably ^a hydrogen atom.

In one polymer, the structural unit having a carboxy group and / or a salt thereof can be used alone or in combination of two or more.
The structural unit having a carboxy group and / or a salt thereof is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 5 to 45 mol%, based on the structural units of all polymer components. -40 mol% is particularly preferable, and 5-35 mol% is most preferable.
In the present invention, when the content of the “structural unit” is defined in terms of molar ratio, the “structural unit” is synonymous with the “monomer unit”. In the present invention, the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

-Structural unit having an epoxy group and / or an oxetanyl group-
The polymer component contains at least a polymer having a structural unit having an epoxy group and / or an oxetanyl group.
A 3-membered cyclic ether group is also called an epoxy group, and a 4-membered cyclic ether group is also called an oxetanyl group.
The structural unit a2-1 having the epoxy group and / or oxetanyl group only needs to have at least one epoxy group or oxetanyl group in one structural unit, and one or more epoxy groups and one or more oxetanyl groups. Group, two or more epoxy groups, or two or more oxetanyl groups may be included, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups. It is more preferable to have one or two oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic epoch Such compounds may be mentioned containing shea skeleton, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Acid esters, and the like, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit a2-1 having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. A monomer is preferred.

  Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyl) Preferred is oxetane-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit having an epoxy group and / or oxetanyl group include the following structural units. R represents a hydrogen atom or a methyl group.

  The content of the structural unit having the epoxy group and / or oxetanyl group in the polymer having the structural unit having the epoxy group and / or oxetanyl group is preferably 5 to 90 mol% with respect to all the structural units of the polymer. 20-80 mol% is more preferable, and 30-70 mol% is still more preferable.

-Other structural units-
In the present invention, each polymer represented by I or II may have other structural units in addition to the two structural units described above.
There is no restriction | limiting in particular as a monomer which forms other structural units, For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Examples thereof include dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, and unsaturated aromatic compounds.
The monomer which forms another structural unit can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the other structural units include styrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4-hydroxybenzoic acid (3 -Methacryloyloxypropyl) ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) Examples of the structural unit include 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, and ethylene glycol monoacetoacetate mono (meth) acrylate. In addition, compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  As other structural units, styrenes or structural units derived from monomers having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.

  In all the structural units constituting the polymer, the content of the other structural units is preferably 60 mol% or less, more preferably 50 mol% or less, and more preferably 40 mol% or less, based on all the structural units of the polymer. Further preferred. As a lower limit, although 0 mol% may be sufficient, it is preferable to set it as 1 mol% or more, for example, and it is more preferable to set it as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

-Molecular weight of polymer-
The molecular weight of each polymer in the polymer component is independently polystyrene-converted weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and 10,000 to 20,000. Is more preferable. Various characteristics are favorable in the said range. The ratio of the number average molecular weight Mn to the weight average molecular weight Mw (dispersity, Mw / Mn) is preferably 1.0 to 5.0, and more preferably 1.5 to 3.5.
In addition, it is preferable to measure the weight average molecular weight and the number average molecular weight in the present invention by a gel permeation chromatography (GPC) method. The measurement by the gel permeation chromatography method in the present invention uses HLC-8020GPC (manufactured by Tosoh Corporation), and TSKgel Super HZ M-H, TSK gel Super HZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation), 4.6 mmID. It is preferable to use THF (tetrahydrofuran) as an eluent.

-Method for producing polymer-
Various methods are also known for the synthesis of the above-mentioned polymer. For example, a radical polymerizable monomer containing a radical polymerizable monomer used to form each structural unit is exemplified. It can be synthesized by polymerizing the mixture in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.

It is preferable that content of the said polymer component in the photosensitive resin composition of this invention is 20-95 mass% with respect to the total organic solid of a photosensitive resin composition, and is 50-93 mass%. More preferably, it is more preferably 55 to 90% by mass. When the content is within this range, an organic film having good curability can be obtained.
The total solid content of the photosensitive resin composition refers to all components excluding the organic solvent, and the total organic solid content of the photosensitive resin composition refers to inorganic components such as silica particles and an organic solvent described later. It means all components except for.

<Quinonediazide compound>
The photosensitive resin composition of the present invention contains a quinonediazide compound.
As the quinonediazide compound, a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with actinic rays can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used. As specific examples of these compounds, for example, the description in paragraphs 0075 to 0078 of JP2012-088459A can be referred to, and the contents thereof are incorporated in the present specification.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2. -Naphthoquinonediazide-4-sulfonic acid amide etc. are also used suitably. Further, 4,4 ′-{1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene} bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) Mol)), 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44 mol), etc. It may be used.

These quinonediazide compounds can be used singly or in combination of two or more.
The content of the quinonediazide compound in the photosensitive resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass with respect to 100 parts by mass of the total organic solid content in the photosensitive resin composition. 10-25 mass parts is still more preferable. By setting the blending amount of the quinonediazide compound within the above range, the difference in solubility between the irradiated portion of the actinic ray and the unirradiated portion with respect to the alkaline aqueous solution serving as the developer is large, the patterning performance is improved, and the resistance of the cured film obtained is improved. Good solvent properties.

<Solvent>
The photosensitive resin composition of the present invention contains a solvent as component C.
The photosensitive resin composition of the present invention includes the polymer component and the quinonediazide compound, which are essential components, and an optional component described below, using an organic solvent in which the polymer component and the quinonediazide compound are dissolved. It is preferable to prepare the photosensitive resin composition as a liquid in which the above components are dissolved and / or dispersed.
As the solvent, known organic solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol. Monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol diacetates, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, alcohols , Esters, ketones, amides, lactones, etc. . As specific examples of these organic solvents, reference can be made to paragraph 0062 of JP-A-2009-098616.

  Preferred examples include propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butylene glycol diacetate, methoxypropyl acetate, cyclohexanol acetate, propylene glycol diacetate, tetrahydroflur Examples include furyl alcohol.

The boiling point of the solvent is preferably from 100 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C, from the viewpoint of applicability.
The solvent which can be used for this invention can be used individually by 1 type or in combination of 2 or more types. It is also preferred to use solvents having different boiling points in combination.
The content of the solvent in the photosensitive resin composition of the present invention is 100 to 3,000 parts by mass per 100 parts by mass of the total organic solid content of the photosensitive resin composition from the viewpoint of adjusting the viscosity to be suitable for coating. It is preferable that it is 200 to 2,000 parts by mass, and more preferably 250 to 1,000 parts by mass.
As solid content concentration of the photosensitive resin composition of this invention, 3-50 mass% is preferable, and it is more preferable that it is 10-40 mass%.

<At least one heterocyclic compound selected from the group consisting of triazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds and benzimidazole compounds>
The photosensitive resin composition of the present invention comprises at least one heterocyclic compound selected from the group consisting of triazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds and benzimidazole compounds (hereinafter referred to as “specific complex”). Also referred to as “ring compound”. The photosensitive resin composition of the present invention contains a specific polymer component, a quinonediazide compound, a specific heterocyclic compound, and a maleimide compound, so that it has excellent developability, hardness of the resulting cured product, and prevention of corrosion on metal wiring. It is estimated that the cured product obtained is excellent in transparency and the transparency of the obtained cured product is also excellent.

  The specific heterocyclic compound is not particularly limited as long as it is a compound having a triazole ring structure, a tetrazole ring structure, a thiadiazole ring structure, a triazine ring structure, a rhodanine ring structure, a thiazole ring structure and / or a benzimidazole ring structure. A compound represented by any one of Formulas D1 to D12 is preferable.

In Formula D1 to Formula D12, R ¹ , R ⁵ , R ⁷ , R ⁹ , R ²⁰ and R ²⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or an amino group, and R ² to R ⁴ , R ⁸ , R ^{10 to} R ¹³ , R ^{15 to} R ¹⁸ , R ²² , R ²⁴ and R ^{26 to} R ²⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, Represents an alkylamino group, an arylamino group, a mercapto group, an alkylthio group or an arylthio group, and R ⁶ , R ¹⁴ , R ²¹ and R ²³ each independently represent a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group; , Alkylamino group, arylamino group, mercapto group, alkylthio group, arylthio group, carboxy group, hydroxy group, alkoxy group or It represents an aryloxy ^{group, R 19} represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n1 to n4 each independently represent an integer of 0 to 4.

  In addition, the compound represented by the formula D1 to the formula D3 is a triazole compound, the compound represented by the formula D4 is a tetrazole compound, the compound represented by the formula D5 to the formula D7 is a thiadiazole compound, The compound represented by the formula D8 is a triazine compound, the compound represented by the formula D9 is a rhodanine compound, the compound represented by the formula D10 is a benzothiazole compound, and is represented by the formula D11. The compound is a benzimidazole compound, and the compound represented by the formula D12 is a thiazole compound.

R ¹ , R ⁷ , R ⁹ , R ²⁰ and R ²⁵ are each independently preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group, Particularly preferred is an atom.
R ⁵ is preferably a hydrogen atom, an alkyl group or an amino group, more preferably a hydrogen atom or an amino group.
R ^{2 to} R ⁴ , R ⁸ , R ^{10 to} R ¹³ , R ^{15 to} R ¹⁸ , R ²² , R ²⁴ and R ^{26 to} R ²⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, An amino group, a mercapto group or an alkylthio group is preferable, and a hydrogen atom, an amino group, a mercapto group or an alkylthio group is more preferable.
R ^{15 to} R ¹⁷ are each independently preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, a mercapto group, or an alkylthio group, more preferably an amino group or a heteroaryl group, Particularly preferred is an amino group or a pyridyl group.
Further, from the viewpoint of synthesis, R ^{15 to} R ¹⁷ are preferably the same group.
R ¹⁸ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, a mercapto group or an alkylthio group, more preferably a hydrogen atom, an amino group, a mercapto group or an alkylthio group, More preferably, it is an atom.
R ⁶ , R ¹⁴ , R ²¹ and R ²³ are each independently an alkyl group, aryl group, heteroaryl group, amino group, alkylamino group, arylamino group, mercapto group, alkylthio group, arylthio group, carboxy group, hydroxy group It is preferably a group, an alkoxy group or an aryloxy group, and more preferably an alkyl group, an aryl group, a heteroaryl group, an amino group, a mercapto group, an alkylthio group, an arylthio group or a carboxy group.
R ⁶ , R ¹⁴ , R ²¹ and R ²³ can be bonded by substituting a hydrogen atom at an arbitrary position on the benzene ring in the above formulas.
R ¹⁹ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
n1 to n4 are each independently preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

The specific heterocyclic compound is preferably at least one heterocyclic compound selected from the group consisting of a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound and a benzimidazole compound from the viewpoint of adhesion. More preferably, it is at least one heterocyclic compound selected from the group consisting of compounds, thiadiazole compounds, rhodanine compounds, thiazole compounds and benzimidazole compounds, and at least one complex selected from the group consisting of tetrazole compounds and thiadiazole compounds. More preferably, it is a ring compound. In addition, the specific heterocyclic compound is preferably a compound represented by any one of the above formulas D1, D2 and D4 to D12 from the viewpoint of adhesion, and any of the above formulas D4 to D12. More preferably, it is a compound represented by any one of the above formulas D4 to D7 and D9 to D12, and it is represented by any one of the above formulas D4 to D7. Particularly preferred is a compound.
The specific heterocyclic compound is preferably at least one heterocyclic compound selected from the group consisting of a thiadiazole compound and a triazine compound, and more preferably a thiadiazole compound, from the viewpoint of preventing corrosion of metal wiring. In addition, the specific heterocyclic compound is preferably a compound represented by any one of the above formulas D5 to D8 from the viewpoint of corrosion resistance of metal wiring, and any one of the above formulas D5, D6, and D8. More preferably, it is a compound represented by the above formula D5, or a compound represented by the above formula D6, more preferably a compound represented by the above formula D6. Particularly preferred.

Specific examples of the specific heterocyclic compound include the following compounds.
Examples of the triazole compound include the following compounds.

  The following compounds can be illustrated as a tetrazole compound.

  Examples of the thiadiazole compound include the following compounds.

  Examples of the triazine compound include the following compounds.

  Examples of the rhodanine compound include the following compounds.

  Examples of the thiazole compound and the benzimidazole compound include the following compounds.

A specific heterocyclic compound may be contained individually by 1 type, or may contain 2 or more types.
Although there is no restriction | limiting in particular in content of the specific heterocyclic compound in the photosensitive resin composition of this invention, It is preferable that it is 0.1-20 mass% with respect to the total organic solid content of the photosensitive resin composition. 0.2 to 10% by mass, more preferably 0.5 to 8% by mass, and particularly preferably 1 to 5% by mass. It is excellent in the hardness of the obtained hardened | cured material and the corrosion prevention property to metal wiring as it is the said range, and it is excellent in the transparency of the hardened | cured material obtained.

<Maleimide compound>
The photosensitive resin composition of the present invention contains a maleimide compound.
The maleimide compound is not particularly limited as long as it is a compound having one or more groups represented by the following formula E, but preferably includes a compound having two or more groups represented by the following formula E, It is more preferable to include a compound having two or more maleimide groups.
In the present invention, a compound having two or more groups represented by the following formula E is a maleimide compound and is not included in the compound having two or more ethylenically unsaturated bonds.

Wherein E, ^{Y 1} is _{-CH = CH -, - C (} CH 3) = CH -, - C (= CH 2) -CH 2 -, _{or, -C (CH 3) = C} (CH 3) - Where the wavy line represents the position of coupling with another structure.

Y ¹ is preferably —CH═CH—, —C (CH ₃ ) ═CH—, or —C (═CH ₂ ) —CH ₂ —, and —CH═CH— or —C ( More preferably, CH ₃ ) ═CH—, and particularly preferably —CH═CH—.
The number of groups represented by the above formula E in the maleimide compound is preferably 1-20, more preferably 1-10, still more preferably 2-8, and preferably 2. Particularly preferred.
Further, from the viewpoint of stability of the compound and the composition, in the maleimide compound, it is preferable that the nitrogen atom of the group represented by the formula E is directly bonded to the aromatic ring.
The maleimide compound preferably includes a compound having two groups represented by the following formula E, that is, a bismaleimide compound, and includes a compound represented by the following formula E1, from the viewpoints of hardness and corrosion resistance. Is more preferable.

In formula E1, each R ^e1 independently represents a single bond, an alkylene group, —SO ₂ —, —SO—, —S— or —O—, and each R ^e2 independently represents a halogen atom or an alkyl group. , M1 represents an integer of 0 to 5, and m2 independently represents an integer of 0 to 4.

R ^e1 is preferably each independently a single bond, an alkylene group having 1 to 8 carbon atoms or —O—, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms or —O—. More preferably, they are a single bond, a methylene group, a dimethylmethylene group (2,2-propylene group) or —O—.
Each R ^e2 is preferably independently an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably a methyl group or an ethyl group.
R ^e1 and R ^e2 can be bonded by substituting a hydrogen atom at an arbitrary position on the benzene ring in the formula E1.
In addition, R ^e1 is preferably bonded at the p-position to the maleimide group or the group having a maleimide group on the benzene ring in the above formula E1.
m1 is preferably an integer of 1 to 5, more preferably an integer of 2 to 5, and still more preferably an integer of 3 to 5.
It is preferable that m2 is an integer of 0-2 each independently.

  Specific examples of the maleimide compound include the following compounds.

Specific examples of the maleimide compound include the following bismaleimide compounds.
1,6-bismaleimide-2,4,4-trimethylhexane, N, N′-decamethylene bismaleimide, N, N′-octamethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N '-Trimethylene bismaleimide, bis [(2,5-dioxo-2,5-dihydropyrrol-1-yl) methyl] bicyclo [2.2.1] heptane, 4,4'-diphenyl ether bismaleimide, 4, 4'-diphenylsulfone bismaleimide, 4,4'-diphenyl sulfide bismaleimide, 3,3'-dimethyl-4,4'-diphenylmethane bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3 -Bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, 3,3 ', 5,5'- Tramethyl-4,4′-diphenylmethane bismaleimide, 3,3′-diethyl-4,4′-diphenylmethane bismaleimide, 3,3′-di-n-butyl-4,4′-diphenylmethane bismaleimide, 3,3 ', 5,5'-tetraethyl-4,4'-diphenylmethane bismaleimide and the like.

A maleimide compound may be contained individually by 1 type, or may contain 2 or more types.
The content of the maleimide compound in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass with respect to the total organic solid content of the photosensitive resin composition. More preferably, it is 5-15 mass%, It is further more preferable that it is 1-10 mass%, It is especially preferable that it is 3-8 mass%. It is excellent in the adhesiveness of the hardened | cured material obtained as it is the said range, and the corrosion prevention property to a metal wiring.

<Silica particles>
The photosensitive resin composition of the present invention preferably contains silica particles. By containing silica particles, the hardness of the resulting cured product is excellent.
In addition, as a result of detailed studies by the present inventors, the present inventors have found that when silica particles are contained, corrosion on the metal wiring is less likely to proceed, but the photosensitive resin composition of the present invention. The inventors have found that by containing the specific heterocyclic compound and the maleimide compound, even if silica particles are contained, the metal wiring is excellent in corrosion resistance.
The average primary particle size of the silica particles used in the present invention is preferably 1 to 200 nm, more preferably 1 to 100 nm, still more preferably 1 to 50 nm, and particularly preferably 1 to 30 nm. The average primary particle diameter refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the maximum outer diameter is taken as the particle diameter of the particle.
Further, from the viewpoint of the hardness of the cured product, the porosity of the silica particles is preferably less than 10%, more preferably less than 3%, and particularly preferably no void. The porosity of the particle is an arithmetic average of 200 of the area ratio between the void portion of the cross-sectional image obtained by an electron microscope and the entire particle.

The silica particles are not particularly limited as long as they are inorganic oxide particles containing silicon dioxide, and particles containing silicon dioxide or a hydrate thereof as a main component (preferably 80% by mass or more) are preferable. The said particle | grains may contain the aluminate as a minor component (for example, less than 5 mass%). Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate.
The silica particles may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. Colloidal silica is exemplified as an example of such silica.
There is no restriction | limiting in particular as a dispersion medium of colloidal silica, Any of water, an organic solvent, and these mixtures may be sufficient. These may be used individually by 1 type and can also use 2 or more types together.
In the present invention, the particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill. When silica particles are introduced into the photosensitive resin composition of the present invention using colloidal silica, it does not mean that the colloidal silica exists in a colloidal state in the composition.

The silica particle may contain only 1 type and may contain 2 or more types.
The content of silica particles is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more with respect to the total solid content of the photosensitive resin composition, from the viewpoint of corrosion prevention and hardness. . Moreover, 80 mass% or less is preferable, 60 mass% or less is more preferable, 50 mass% or less is further more preferable, and less than 40 mass% is especially preferable.

<Adhesion promoter>
The photosensitive resin composition of the present invention preferably contains an adhesion promoter.
As the adhesion promoter, a known adhesion promoter can be used, and an alkoxysilane compound is preferable. When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved.
The alkoxysilane compound is not particularly limited as long as it has at least one group in which an alkoxy group is directly bonded to a silicon atom, but may be a compound having a dialkoxysilyl group and / or a trialkoxysilyl group. Preferably, it is a compound having a trialkoxysilyl group.
The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention includes a base material, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, molybdenum, titanium, and aluminum, and a cured film. It is preferable that it is a compound which improves adhesiveness. Specifically, a known silane coupling agent or the like is also effective. A silane coupling agent having an ethylenically unsaturated bond is preferred.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxypropyl. Trialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane It is done. Of these, γ-methacryloxypropyltrialkoxysilane, γ-acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, and γ-glycidoxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
Examples of commercially available products include KBM-403 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.

The adhesion promoter may contain only one type or two or more types.
The content of the adhesion promoter in the photosensitive resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 2 to 20% by mass, based on the total organic solid content of the photosensitive resin composition. More preferred is ˜15% by mass. When two or more types of adhesion promoters are included, the total amount is preferably within the above range.

<Surfactant>
The photosensitive resin composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. As the surfactant, nonionic surfactants are preferable, and fluorine-based surfactants are more preferable.
Examples of the surfactant that can be used in the present invention include commercially available products, such as Megafac F142D, F172, F173, F176, F177, F183, F479, F482, F554, and F780. F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S -141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-1 05, the same SC-106 (Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (Mitsubishi Materials Electronics Chemical Co., Ltd.), and Footent 250 (Neos Co., Ltd.). . In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), MegaFuck (manufactured by DIC Corporation) , FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

  Moreover, as surfactant, the compound of Unexamined-Japanese-Patent No. 2014-238438 Paragraph 0151-0155 can also be mentioned as a preferable example.

When blended, the content of the surfactant in the photosensitive resin composition of the present invention is preferably 0.001 to 5.0 parts by mass with respect to 100 parts by mass in the total organic solid content of the photosensitive resin composition. 0.01 to 2.0 parts by mass is more preferable.
Only one type of surfactant may be included, or two or more types of surfactants may be included. When two or more types are included, the total amount is preferably within the above range.

<Sensitizer>
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to accelerate the decomposition in combination with the quinonediazide compound.
The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the quinonediazide compound, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the quinonediazide compound undergoes a chemical change to generate an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (Eg, merocyanine, carbomerocyanine), rhodocyanins, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridineo , Chloroflavin, acriflavine), acridones (for example, acridone, 10-butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squaliums (for example, squalium), styryls, base styryls ( For example, 2- {2- [4- (dimethylamino) phenyl] ethenyl} benzoxazole), coumarins (eg, 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2, 3, 6 , 7-tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11-non).

A sensitizer may be used individually by 1 type and can also use 2 or more types together.
The content of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by mass, and 10 to 500 parts by mass with respect to 100 parts by mass of the quinonediazide compound of the photosensitive resin composition. More preferably, it is more preferably 50 to 200 parts by mass.

<Crosslinking agent>
The photosensitive resin composition of the present invention may contain a crosslinking agent.
The crosslinking agent is preferably a crosslinking agent having a molecular weight of 1,000 or less.
The crosslinking agent can be used without limitation as long as a crosslinking reaction is caused by heat (however, the polymer and the alkoxysilyl compound are excluded). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, a compound having two or more blocked isocyanate groups in the molecule (a compound having a protected isocyanate group), and two in the molecule It is preferable to include at least one compound selected from the group consisting of the above-mentioned compound having an alkoxymethyl group and a compound having at least one ethylenically unsaturated group, and two or more epoxy groups in the molecule Or it is more preferable that at least 1 sort (s) chosen from the group which consists of a compound which has an oxetanyl group, and two or more blocked isocyanate compounds in a molecule | numerator is included.

The content of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0 to 30% by mass and more preferably 1 to 20% by mass with respect to the total organic solid content of the photosensitive resin composition. preferable.
The said crosslinking agent can also use multiple types together, In that case, addition amount is calculated by the total content which added all the crosslinking agents.
Below, the crosslinking agent preferably used in this invention is demonstrated.

-Compounds having two or more epoxy groups or oxetanyl groups in the molecule-
Examples of the compound having two or more epoxy groups or oxetanyl groups in the molecule include polyfunctional 3- and / or 4-membered cyclic ether compounds. That is, it means a compound having two or more epoxy groups and / or oxetanyl groups in one molecule. The molecular weight of this compound is preferably 1,000 or less. A small amount of an oligomer having a molecular weight of more than 1,000 and less than 5,000, or a polymer having a molecular weight of 5,000 or more may be used in combination with this low-molecular crosslinking agent.

Specific examples of the compound having two or more epoxy groups in the molecule include aliphatic epoxy compounds.
These are available as commercial products. For example, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321 , EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX -920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301 DLC-402 (manufactured by Nagase ChemteX Corporation), Celoxide 2021P, 2081, 3000, EHPE3 50, Epolead GT400, Serubinasu B0134, B0177 (or, Ltd. Daicel), and the like.
These can be used alone or in combination of two or more.

  As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.

  In addition, the compound containing two or more oxetanyl groups in the molecule is preferably used alone or mixed with a compound containing two or more epoxy groups in the molecule.

-A compound having two or more blocked isocyanate groups in the molecule-
In the photosensitive resin composition of the present invention, as the component D, a compound having two or more blocked isocyanate groups in the molecule (also simply referred to as “block isocyanate compound”) can be preferably employed. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group in which the isocyanate group is chemically protected. The blocked isocyanate compound also uses a compound having a molecular weight of 1,000 or less as a crosslinking agent.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that the said blocked isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic. Polyisocyanate may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, Isocyanate compounds such as hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate In addition, a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the matrix structure of the block isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples include aniline, diphenylamine, ethyleneimine, and polyethyleneimine. it can.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate. Examples of the pyrazole compound include pyrazole, methylpyrazole, and dimethylpyrazole.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

  The blocked isocyanate compound that can be used in the present invention is available as a commercial product. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, Nippon Polyurethane Industry Co., Ltd.) Manufactured), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, Mitsui Chemicals, Inc.), Duranate 17B-60PX 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, Asahi Kasei Chemicals Corporation) Manufactured), Death Module BL1100, BL12 5 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) Can do.

-Compounds having two or more alkoxymethyl groups in the molecule-
As the compound having two or more alkoxymethyl groups in the molecule, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of outgas generation amount, A methyl group is particularly preferred.
Among these compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
The alkoxymethyl group-containing crosslinking agent also uses a compound having a molecular weight of 1,000 or less in the photosensitive resin composition.
These compounds having two or more alkoxymethyl groups in the molecule are commercially available, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272. , 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

-Compound having at least one ethylenically unsaturated group-
As the compound having at least one ethylenically unsaturated group, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate is preferably used. it can.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
These compounds having at least one ethylenically unsaturated double bond are used singly or in combination of two or more.
Moreover, when adding the compound which has at least 1 ethylenically unsaturated double bond, it is preferable to add the below-mentioned thermal radical generator.

<Basic compound>
The photosensitive resin composition of the present invention may contain a basic compound.
The basic compound is not particularly limited, and examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include compounds described in paragraphs 0204 to 0207 of JP2011-221494A.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene, butane-1,2,3,4-tetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
Among these, a heterocyclic amine is preferable, and N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea is particularly preferable.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more.
It is preferable that content of the basic compound in the photosensitive resin composition of this invention is 0.001-3 mass% with respect to the total organic solid content in the photosensitive resin composition, 0.05-0 More preferably, it is 5 mass%.

<Antioxidant>
The photosensitive resin composition of the present invention preferably contains an antioxidant.
As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Of these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing film thickness, with phenol-based antioxidants being the most preferred. preferable. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, the contents of which are incorporated herein.

  Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 , ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS 90, ADK STAB ZS 90 -91 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Company, Ltd.), Tinuvin 405 (manufactured by BASF), and the like. Among them, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035, Irganox 1098, and Tinuvin 405 can be preferably used.

It is preferable that content of the antioxidant in the photosensitive resin composition of this invention is 0.1-10 mass% with respect to the total organic solid of a photosensitive resin composition, 0.2-5 mass% It is more preferable that it is 0.5-4 mass%. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
Further, as additives other than antioxidants, various ultraviolet absorbers described in "New Development of Polymer Additives" (Nikkan Kogyo Shimbun Co., Ltd.), metal deactivators, and the like are used as photosensitive resin compositions. You may add to.

<Other ingredients>
In addition to the above components, the photosensitive resin composition of the present invention includes, as necessary, an ultraviolet absorber, a metal deactivator, an acid proliferator, a development accelerator, a plasticizer, a polymerization inhibitor, a thermal radical. Known additives such as generators, thermal acid generators, thickeners, and organic or inorganic suspending agents can be added. Moreover, as these compounds, the description of Paragraph 0201-0224 of Unexamined-Japanese-Patent No. 2012-88459, and Unexamined-Japanese-Patent No. 2014-238438 can also be considered, for example, These content is integrated in this-application specification.

(Hardened product and manufacturing method thereof)
The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. The cured product is preferably a cured film. Moreover, it is preferable that the hardened | cured material of this invention is a cured film obtained by the manufacturing method of the hardened | cured material of this invention.
The method for producing a cured product of the present invention is not particularly limited as long as it is a method for producing a cured product by curing the photosensitive resin composition of the present invention, but includes the following steps a to d in this order. Is preferred.
Step a: Application step of applying the photosensitive resin composition of the present invention onto the substrate Step b: Solvent removal step of removing the solvent from the applied photosensitive resin composition Step c: Photosensitive resin composition from which the solvent has been removed Exposure step of exposing at least a part of the product with actinic rays Step d: Heat treatment step of heat-treating the exposed photosensitive resin composition In addition, the method for producing a cured product of the present invention includes a step c and a step d. More preferably, the following step e is included.
Step e: Development step of developing the exposed photosensitive resin composition with an aqueous developer

In the said application | coating process, it is preferable to apply | coat the photosensitive resin composition of this invention on a board | substrate, and to make a wet film | membrane containing a solvent. Before applying the photosensitive resin composition to the substrate, the substrate can be cleaned such as alkali cleaning or plasma cleaning. Furthermore, the substrate surface can be treated with hexamethyldisilazane or the like after cleaning the substrate. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
Resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester resin, cyclic polyolefin, Synthetic trees such as aromatic ether resin, maleimide-olefin copolymer, cellulose, episulfide resin A substrate made of, and the like.
These substrates are rarely used in the above-described form, and usually have a multilayer structure such as a TFT (Thin-Film Transistor) element, depending on the form of the final product.
In the case of an on-cell touch panel or the like, the photosensitive resin composition of the present invention is applied to a liquid crystal display (LCD) cell or an organic light emitting diode (OLED) cell that has been once completed as a panel. You can also.

  Since the photosensitive resin composition of this invention is excellent in the corrosion prevention property to a metal wiring, as a board | substrate, what has a metal wiring is preferable. The metal in the metal wiring may be titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium, oxides or alloys thereof, or a laminate thereof. Preferably, molybdenum, titanium, aluminum, copper, alloys thereof, or laminates thereof are more preferable, and copper, copper alloys, and molybdenum / aluminum / molybdenum laminates are particularly preferable. The effect of this invention can be exhibited more as it is the said aspect. In addition, a metal and a metal oxide may be used individually by 1 type, or may use multiple types together.

  The coating method on the substrate is not particularly limited. For example, a method such as an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or a printing method may be used. it can.

In the solvent removal step, it is preferable to remove the solvent from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. Moreover, in the said solvent removal process, it is not necessary to remove the solvent in the photosensitive resin composition completely, and at least one part should just be removed.
In addition, the said application | coating process and the said solvent removal process may be performed in this order, may be performed simultaneously, or may be repeated alternately. For example, after all of the inkjet application in the application step is completed, the solvent removal step may be performed, or the substrate is heated and the photosensitive resin composition is discharged by the inkjet application method in the application step. Solvent removal may be performed.

The said exposure process is a process of generating an acid from a quinonediazide compound using actinic rays, and making the exposed part irradiated with actinic rays developable.
“Actinic light” in the present invention is not particularly limited as long as it is an active energy ray capable of imparting an energy capable of generating an acid from a quinonediazide compound by irradiation, and widely used for α rays, γ rays, X It includes rays, ultraviolet rays (UV), visible rays, electron beams, and the like.
In the exposure step, it is preferable to irradiate the obtained coating film with an actinic ray having a wavelength of 300 nm to 450 nm in a predetermined pattern.
As an exposure light source that can be used in the exposure process, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, and the like can be used. Actinic rays having a wavelength of from 300 nm to 450 nm, such as h-line (405 nm) and g-line (436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
The exposure in the exposure step is preferably performed in a state where oxygen is blocked from the viewpoint of curing acceleration. Examples of means for blocking oxygen include exposure in a nitrogen atmosphere and exposure with an oxygen blocking film.
Moreover, the exposure in the said exposure process should just be performed to at least one part of the photosensitive resin composition from which the solvent was removed.

In addition, post-exposure heat treatment (hereinafter also referred to as “PEB”) can be performed after the exposure step and before the development step. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
The heating method is not particularly limited, and a known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned.
The heating time is preferably about 1 to 30 minutes in the case of a hot plate, and is preferably about 20 to 120 minutes in other cases. If it is the said temperature range, it can suppress and damage to a board | substrate and an apparatus, and can heat.

Moreover, it is more preferable that the manufacturing method of the hardened | cured material of this invention includes the image development process which develops the exposed photosensitive resin composition with an aqueous developing solution between the said exposure process and the said heat processing process.
In the development step, the uncured photosensitive resin composition is developed and removed using an aqueous developer to form a negative image. The developer used in the development step is preferably an alkaline aqueous developer.
The developer used in the development step preferably contains a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0]- Alicyclic amines such as 5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
As a preferred developing solution, a 0.4 to 2.5% by mass aqueous solution of tetramethylammonium hydroxide can be mentioned.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dip method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.
For pattern exposure and development, a known method or a known developer can be used. For example, the pattern exposure method and the development method described in JP 2011-186398 A and JP 2013-83937 A can be suitably used.

It is preferable that the manufacturing method of the cured film of this invention includes the heat processing process (post-baking) which heat-processes the exposed photosensitive resin composition after the said exposure process, Preferably after the said image development process. By performing the heat treatment after developing the photosensitive resin composition of the present invention, a cured film having higher strength can be obtained.
As heat processing temperature in the said heat processing process, 180 degrees C or less is preferable, 150 degrees C or less is more preferable, and 130 degrees C or less is still more preferable. As a lower limit, 80 degreeC or more is preferable and 90 degreeC or more is more preferable. The heating method is not particularly limited, and a known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned.
The heating time is preferably about 1 to 30 minutes in the case of a hot plate, and is preferably about 20 to 120 minutes in other cases. If it is the said temperature range, it can harden | cure, suppressing the damage to a board | substrate and an apparatus.
In addition, the heat treatment step can be performed after baking at a relatively low temperature before the heat treatment step (post-bake) (addition of a middle bake step). When performing middle baking, it is preferable to heat-treat at a temperature of 100 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Further, middle baking and post baking can be heated in three or more stages. The shape of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film (insulating film) or an overcoat film (protective film), more preferably used as an overcoat film for a touch panel, and as an overcoat film for an on-cell structure touch panel. Further preferably used. The on-cell touch panel is synonymous with an on-cell touch panel display device described later. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this invention.
By the photosensitive resin composition of the present invention, a cured film having sufficient hardness even when cured at a low temperature, for example, a cured film having a hardness of H or more can be obtained. Since the protective film formed by curing the photosensitive resin composition of the present invention is excellent in cured film properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
Especially, the cured film of this invention can be used suitably as a protective film for touchscreen wiring, and can be used more suitably as a protective film for wiring in an on-cell structure touchscreen.

  Since the photosensitive resin composition of the present invention is excellent in curability and cured film properties, a cured product or resist pattern obtained by curing the photosensitive resin composition of the present invention as a structural member of a device for MEMS (Micro Electro Mechanical Systems). Is used as a partition wall or as a part of a mechanical drive part. Examples of such MEMS devices include SAW (Surface Acoustic Wave) filters, BAW (Bulk Acoustic Wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, Examples include parts such as biochips and sealants. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

  Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP2011-107476A, JP2010-2010A. Partition wall (12) and planarization film (102) described in FIG. 4A of JP-A-9793, and bank layer (221) and third interlayer insulating film (FIG. 10 of JP 2010-27591A). 216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4 (a) of Japanese Patent Laid-Open No. 2009-128577, and FIG. 3 of Japanese Patent Laid-Open No. 2010-182638. It can also be used to form a planarization film (12) and a pixel isolation insulating film (14). In addition, spacers for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, color filters for the liquid crystal display device, color filter protective films, facsimiles, electronic copying machines, imaging of on-chip color filters such as solid-state image sensors It can also be suitably used for a microlens of an optical system or an optical fiber connector.

(Display device and touch panel)
The display device of the present invention has the cured film of the present invention.
Examples of the display device of the present invention include various display devices such as an organic EL display device, a liquid crystal display device, and a touch panel display device.

The organic EL display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic materials having various structures. An EL display device and a liquid crystal display device can be given.
For example, specific examples of TFTs included in the organic EL display device of the present invention include amorphous silicon TFTs, low-temperature polysilicon TFTs, and oxide semiconductor TFTs. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 1 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. A wiring 2 such as a metal wiring is for connecting the TFT 1 to an organic EL element formed between TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing film 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix type in which two electrodes are formed, sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and TFTs 1 for driving the organic EL elements are connected. An organic EL display device is obtained.

The liquid crystal display device of the present invention has the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has an overcoat film (protective film) formed using the photosensitive resin composition of the present invention, a planarizing film, and an interlayer insulating film. A known liquid crystal display device having a structure can be given.
For example, as specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention, amorphous silicon TFT, low temperature polysilicon TFT, oxide semiconductor TFT (for example, indium gallium zinc oxide, so-called, IGZO) and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Vertical Alignment) method, IPS (In-Plane-Switching) method, FFS (Fringe Field Switching) method, OCB (OCB) method. Optically Compensated Bend) method.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of Japanese Patent Laid-Open No. 2005-284291, -346054 can be used as the organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that can be taken by the liquid crystal display device of the present invention include a rubbing alignment method and a photo alignment method. Further, the polymer alignment may be supported by the PSA (Polymer Sustained Alignment) technique described in JP2003-149647A or JP2011-257734A.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to a planarization film and an interlayer insulating film, it is suitable for a protective film, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, etc. Can be used.

FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type (touch panel display device). Further, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP2011-145686A or the interlayer insulating film (520) described in JP2009-258758A. Can do.

The touch panel of the present invention is a touch panel in which all or part of the insulating layer and / or protective layer is made of a cured product of the photosensitive resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. As the touch panel of the present invention, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, and an electromagnetic induction method may be used. Among these, the electrostatic capacity method is preferable.
Examples of the capacitive touch panel include those disclosed in JP 2010-28115 A and those disclosed in International Publication No. 2012/057165.
As a touch panel display device, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 of Japanese Patent Publication No. 2012-517051), a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2012-43394). 14, International Publication No. 2012/141148, FIG. 2 (b)), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type, and other configurations (for example, the figure of JP2013-164871A) 6).
FIG. 3 is a conceptual diagram illustrating an example of a touch panel display device.
For example, the cured film of the present invention is preferably applied to the protective film between the layers in FIG. 3, and is also preferably applied to an interlayer insulating film that separates the detection electrodes of the touch panel. In addition, as a detection electrode of a touch panel, it is preferable that they are silver, copper, aluminum, titanium, molybdenum, and these alloys.
In FIG. 3, reference numeral 110 denotes a pixel substrate, 140 denotes a liquid crystal layer, 120 denotes a counter substrate, and 130 denotes a sensor unit. The pixel substrate 110 includes a polarizing plate 111, a transparent substrate 112, a common electrode 113, an insulating layer 114, a pixel electrode 115, and an alignment film 116 in order from the lower side of FIG. The counter substrate 120 includes an alignment film 121, a color filter 122, and a transparent substrate 123 in order from the lower side of FIG. The sensor unit 130 includes a retardation film 124, an adhesive layer 126, and a polarizing plate 127. In FIG. 3, reference numeral 125 denotes a sensor detection electrode. The cured film of the present invention includes an insulating layer (114) (also referred to as an interlayer insulating film) in the pixel substrate portion, various protective films (not shown), various protective films (not shown) in the pixel substrate portion, and a counter substrate portion. Can be used for various protective films (not shown), various protective films (not shown) for the sensor portion, and the like.

  In addition, a statically driven liquid crystal display device can display a pattern with high designability by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A No. 2001-125086.

FIG. 4 is a conceptual diagram of the configuration of another example of the touch panel display device.
A lower display panel 200 corresponding to a thin film transistor display panel provided with a thin film transistor (TFT) 440, and a color filter display panel provided with a plurality of color filters 330 on the surface facing the lower display panel 200 and facing the lower display panel 200. And the liquid crystal layer 400 formed between the lower display panel 200 and the upper display panel 300. The liquid crystal layer 400 includes liquid crystal molecules (not shown).

  The lower display panel 200 is disposed on the first insulating substrate 210, the thin film transistor (TFT) disposed on the first insulating substrate 210, the insulating film 280 formed on the upper surface of the thin film transistor (TFT), and the insulating film 280. A pixel electrode 290 is included. The thin film transistor (TFT) may include a gate electrode 220, a gate insulating film 240 covering the gate electrode 220, a semiconductor layer 250, ohmic contact layers 260 and 262, a source electrode 270, and a drain electrode 272. A contact hole 282 is formed in the insulating film 280 so that the drain electrode 272 of the thin film transistor (TFT) is exposed.

  The upper display panel 300 is disposed on one surface of the second insulating substrate 310, on the light shielding members 320 arranged in a matrix, the alignment film 350 disposed on the second insulating substrate 310, and the alignment film 350. A color filter 330 to be disposed, and a common electrode 370 disposed on the color filter 330 and corresponding to the pixel electrode 290 of the lower display panel 200 to apply a voltage to the liquid crystal layer 400 are included.

  In the touch panel display device shown in FIG. 4, a sensing electrode 410, an insulating film 420, a drive electrode 430, and an insulating film (protective film) 280 are disposed on the other surface of the second insulating substrate 310. As described above, in the manufacture of the liquid crystal display device shown in FIG. 4, when the upper display panel 300 is formed, the sensing electrode 410, the insulating film 420, the drive electrode 430, and the like, which are constituent elements of the touch screen, are formed together. be able to. In particular, a cured film obtained by curing the photosensitive resin composition of the present invention can be suitably used for the insulating film 280 and the insulating film 420.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
St: Styrene (Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
DCPMA: Dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis Example 1: Synthesis of Resin A>
In a flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) and diethylene glycol ethyl methyl ether (Toho Chemical Co., Ltd.) 200 parts by mass (manufactured by Hisolv EDM-S) was charged. Subsequently, 100 parts by mass of monomer (25 molar equivalents of styrene, 20 molar equivalents of methacrylic acid, 45 molar equivalents of glycidyl methacrylate and 10 molar equivalents of dicyclopentanyl methacrylate) were charged, and the mixture was gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the resin A. The solid content concentration of the obtained polymer solution was adjusted to 37.9% by mass.

<Synthesis Examples 2 to 11: Synthesis of Resins B to K>
The monomers were changed as shown in Table 1 below, and the resins B to K were synthesized in the same manner as the resin A.

  The unit of the numerical value in each monomer column described in Table 1 is mol%.

Moreover, the detail of the various components used in the Example and the comparative example other than said resin AK is shown below.
Resin L: Cresol novolak resin (cresol / formaldehyde novolak resin, m-cresol / p-cresol (molar ratio) = 60/40, polystyrene equivalent weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Co., Ltd., trade name "EP4020G"
B-1: The following quinonediazide compound (NQD), TAS-200 manufactured by Toyo Gosei Co., Ltd., esterification rate 66%, 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, NQD of α-dimethylbenzyl} phenol skeleton
B-2: TAS-250 manufactured by Toyo Gosei Kogyo Co., Ltd., esterification rate 83%, 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl} phenol skeleton NQD
B-3: 4,4 ′-{1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene} bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensation product with sulfonic acid chloride (3.0 mol) B-4: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (2.0 mol) B-5: 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44) Mole)

Propylene glycol monomethyl ether acetate (PGMEA): Solvent, manufactured by Daicel Corporation T-1 to T-12: The following heterocyclic compounds

  M-1 to M-5: The following maleimide compounds

Silica particles: colloidal silica (average primary particle size 20 nm) dispersion, solid content concentration 30.0% by mass, PMA-ST manufactured by Nissan Chemical Industries, Ltd.
Adhesion promoter S-1: 3-triethoxysilylpropyl isocyanate, Shin-Etsu Chemical Co., Ltd. KBM-9007
Surfactant: Perfluoroalkyl group-containing nonionic surfactant (2% PGMEA solution), Megafac F-554 manufactured by DIC Corporation

Example 1
<Preparation of photosensitive resin composition>
Prepared as follows.
Propylene glycol monomethyl ether acetate (PGMEA): 283.8 partsResin A: 179.2 parts (solid content 67.9 parts)
NQD: 20.0 parts Adhesion promoter S-1: 5.0 parts Maleimide compound M-1: 5.0 parts Heterocyclic compound T-2: 2.0 parts Surfactant: 5.0 Parts (solid content 0.1 parts)
The above components were mixed and stirred with a magnetic stirrer for 1 hour.
Subsequently, it filtered with a 0.45 micrometer membrane filter, and produced the photosensitive resin composition of Example 1 (solid content of 20 mass%).

(Examples 2-35 and Comparative Examples 1-12)
The photosensitive resin compositions of Examples 2 to 35 and Comparative Examples 1 to 12 were the same as in Example 1 except that the components other than the surfactant were changed to the respective components and addition amounts shown in Table 2. Each product was prepared. In addition, solid content concentration was adjusted so that it might become 20 mass% with PGMEA which is a solvent.

-Evaluation-
<Evaluation of corrosion prevention for metal wiring>
A photosensitive resin composition is applied on a substrate obtained by sputtering the following base material I or base material II on a 4-inch silicon wafer, dried (prebaked) in an oven at 90 ° C. for 100 seconds, and has a film thickness of 2.0 μm. A film was formed. Thereafter, the entire surface was exposed to 500 mJ / cm ² (illuminance was 20 mW / cm ² ) and heated (post-baked) at 150 ° C. for 60 minutes in an oven.
The base material I used was obtained by sputtering 10 nm of Ti on a 10 cm × 10 cm glass substrate and then sputtering Cu by 200 nm. The base material II was made of 50 nm Mo and Al on a 10 cm × 10 cm glass substrate. 200 nm and Mo are sputtered in the order of 50 nm.
Artificial sweat having the following composition was dropped onto this substrate, left for one day and night, and then placed in a constant temperature and humidity layer at a temperature of 85 ° C. and a humidity of 85% RH, and the time until corrosion occurred was evaluated according to the following criteria.
1: Less than 24 hours 2: More than 24 hours and less than 78 hours 3: More than 78 hours and less than 150 hours 4: More than 150 hours and less than 300 hours 5: More than 300 hours

-Composition of artificial sweat-
・ Pure water: 100.000 g
・ Sodium chloride: 1.000 g
・ Lactic acid: 0.100 g
・ Disodium hydrogen phosphate anhydride: 0.025 g
L-histidine hydrochloride monohydrate: 0.025g

<Evaluation of hardness>
A photosensitive resin composition is spin-coated on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning), dried in a 90 ° C. oven for 100 seconds (prebaked), and a film having a thickness of 1.0 μm Formed. Thereafter, the entire surface was exposed to 500 mJ / cm ² (illuminance was 20 mW / cm ² ) and heated (post-baked) at 150 ° C. for 60 minutes in an oven.
The substrate was measured for pencil hardness according to JIS K5600-5-4. The pencil used was Uni manufactured by Mitsubishi Pencil Co., Ltd., the load during measurement was 750 g, the load during measurement was 750 g, and the pencil angle was 45.
1: HB or less 2: H
3: 2H
4: Over 3H

<Evaluation of transmittance (transparency)>
A photosensitive resin composition is slit-coated on a 1,000 mm × 1,000 mm glass substrate (trade name: XG, manufactured by Corning) and dried (prebaked) in an oven at 90 ° C. for 100 seconds. A 0 μm film was formed. Thereafter, the entire surface was exposed to 500 mJ / cm ² (illuminance was 20 mW / cm ² ) and heated (post-baked) at 150 ° C. for 60 minutes in an oven.
The transmittance of the substrate at a wavelength of 400 nm was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) using the glass substrate (trade name: XG, manufactured by Corning) as a reference.
1: Transmittance is less than 90% 2: Transmittance is 90% or more and less than 95% 3: Transmittance is 95% or more

<Development evaluation>
The photosensitive resin composition was applied on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) so as to have a film thickness of 2.0 μm, and dried (prebaked) in an oven at 90 ° C. for 100 seconds. Thereafter, exposure was performed at a line and space of 50 μm of 200 mJ / cm ² (illuminance was 24 mW / cm ² ), and developed at 25 ° C. for 30 seconds using an alkali developer (tetramethylammonium hydroxide 0.4 mass% aqueous solution). .

-Linearity evaluation-
The linearity of the line edge part was confirmed with an optical microscope for the developed substrate produced with a 50 μm line and space. The evaluation criteria are shown below.
1: The pattern was not formed because it did not dissolve in the developer. 2: The rattling was almost entirely in the plane of the line edge portion. There is almost no rattling

-Undercut evaluation-
About the board | substrate after the development produced with a 50 micrometer line and space, the condition of the undercut which is the groove | channel or dent which arises in the line pattern side surface in the interface of a board | substrate and a pattern was observed with the scanning electron microscope (SEM).
1: The pattern could not be formed because it did not dissolve in the developer. 2: The undercut was included. 3: The undercut was not included.

  The evaluation results are summarized in Table 3.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: flattening film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12 : Backlight unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter, 110: Pixel substrate, 111: Polarizing plate 112: transparent substrate, 113: common electrode, 114: insulating layer, 115: pixel electrode, 116: alignment film, 120: counter substrate, 121: alignment film, 122: color filter, 123: transparent substrate, 124: phase difference Film: 125: Detection electrode for sensor, 126: Adhesive layer, 127: Polarizing plate, 130: Sensor part, 140: Liquid crystal layer, 200: Lower display panel, 210: First insulating substrate, 20: gate electrode, 240: gate insulating film, 250: semiconductor layer, 260, 262: ohmic contact layer, 270: source electrode, 272: drain electrode, 280: insulating film, 282: contact hole, 290: pixel electrode, 300 : Upper display board, 310: second insulating substrate, 320: light shielding member, 330: color filter, 350: alignment film, 370: common electrode, 400: liquid crystal layer, 410: sensing electrode, 420: insulating film, 430: driving Electrode, 440: TFT

Claims (14)

A polymer component satisfying at least one of the following I and II;
A quinonediazide compound,
Solvent,
At least one heterocyclic compound selected from the group consisting of triazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds and benzimidazole compounds;
A photosensitive resin composition comprising a maleimide compound.
I: a polymer component comprising a polymer having a structural unit having a carboxy group and / or a salt thereof, and a structural unit having an epoxy group and / or an oxetanyl group II: a structural unit having a carboxy group and / or a salt thereof Polymer component including polymer having polymer and polymer having constitutional unit having epoxy group and / or oxetanyl group The photosensitive resin composition according to claim 1, wherein the heterocyclic compound is a compound represented by any one of the following formulas D1 to D12.

In Formula D1 to Formula D12, R ¹ , R ⁵ , R ⁷ , R ⁹ , R ²⁰ and R ²⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or an amino group, and R ² to R ⁴ , R ⁸ , R ^{10 to} R ¹³ , R ^{15 to} R ¹⁸ , R ²² , R ²⁴ and R ^{26 to} R ²⁸ are each independently a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, Represents an alkylamino group, an arylamino group, a mercapto group, an alkylthio group or an arylthio group, and R ⁶ , R ¹⁴ , R ²¹ and R ²³ each independently represent a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group; , Alkylamino group, arylamino group, mercapto group, alkylthio group, arylthio group, carboxy group, hydroxy group, alkoxy group or It represents an aryloxy ^{group, R 19} represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n1 to n4 each independently represent an integer of 0 to 4. The photosensitive resin composition of Claim 1 or 2 in which the said maleimide compound contains the compound represented by the following formula E1.

In formula E1, each R ^e1 independently represents a single bond, an alkylene group, —SO ₂ —, —SO—, —S— or —O—, and each R ^e2 independently represents a halogen atom or an alkyl group. , M1 represents an integer of 0 to 5, and m2 independently represents an integer of 0 to 4.   The photosensitive resin composition of any one of Claims 1-3 which further contains a silica particle.   The photosensitive resin composition of Claim 4 whose average primary particle diameter of the said silica particle is 1-50 nm.   The photosensitive resin composition of Claim 4 or 5 whose content of the said silica particle is 5 to less than 40 mass% with respect to the total solid of the photosensitive resin composition.   The photosensitive resin composition of Claim 2 whose said heterocyclic compound is a compound represented by either the said Formula D1, Formula D2, and Formula D4-Formula D12.   The photosensitive resin composition according to claim 7, wherein the heterocyclic compound is a compound represented by any one of Formulas D4 to D12. The manufacturing method of hardened | cured material which contains at least process a-process d in this order.
Step a: Application step of applying the photosensitive resin composition according to any one of claims 1 to 8 on the substrate Step b: Solvent removal step of removing the solvent from the applied photosensitive resin composition Step c : An exposure step of exposing at least a part of the photosensitive resin composition from which the solvent has been removed with actinic rays step d: a heat treatment step of heat-treating the exposed photosensitive resin composition The manufacturing method of the hardened | cured material of Claim 9 including the process e between the process c and the process d.
Step e: Development step of developing the exposed photosensitive resin composition with an aqueous developer   The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-8.   The cured film according to claim 11, which is an interlayer insulating film or an overcoat film.   A display device comprising the cured film according to claim 11.   A touch panel having the cured film according to claim 11.

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