JP6483382B2 - Photosensitive resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a photosensitive resin composition (hereinafter, also simply referred to as “composition”) and a cured product thereof, and specifically relates to a photosensitive resin composition having excellent base generating ability and a cured product thereof.

  In general, a photosensitive resin composition is obtained by adding a photoinitiator to a photosensitive resin and can be polymerized, cured, or developed by irradiation with energy rays (light). It is used for various photoresists, photo-curing adhesives and the like.

  Photoinitiators are classified into photoradical generators, photoacid generators, and photobase generators, depending on the active species generated by energy beam (light) irradiation. The photo radical generator has advantages such as a high curing rate and no active species remaining after curing. However, since the inhibition of curing by oxygen occurs, there is a disadvantage in that it is necessary to provide a layer for blocking oxygen in curing the thin film. The photoacid generator has the advantage that it is not inhibited by oxygen, but it has the disadvantage that the active species of acid remains to corrode the metal substrate or denature the cured resin. Have. On the other hand, photobase generators are attracting attention because they hardly cause problems such as curing inhibition by oxygen and corrosion by residual active species. However, it generally has a problem of low sensitivity (low curability) as compared with the photoacid generator. Various photobase generators have been proposed so far, and examples of prior art include Patent Documents 1 to 3 and the like.

Special table 2001-513765 gazette International Publication WO 2010/064631 International Publication WO2010 / 064632

  However, the present situation is that even the conventionally proposed photobase generators do not necessarily have sufficient base generating ability. Therefore, in the future, a photobase generator having an excellent base generating ability is indispensable in order to obtain a high-performance photocurable ink, a photosensitive printing plate, various photoresists, a photocurable adhesive, and the like.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition, a cured product thereof, and a novel compound having an excellent base generating ability used therein.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has a high base generating ability as a photoinitiator, and a compound having a specific structure is used as a photobase generator. The present inventors have found that the problem can be solved and have completed the present invention.

（一般式（１）中、環Ａ^１は、下記部分構造式（１−１）〜（１−１０）、の何れかであり、Ｒ^１およびＲ^２は、それぞれ独立に、水素原子、無置換若しくは置換基を有している炭素原子数１〜２０の炭化水素基、またはＲ^１およびＲ^２が、互いに連結して形成する窒素原子を含む環であり、該環にはベンゼン環が縮環していてもよい。）で表される化合物を少なくとも１種含有することを特徴とするものである。

（式中、＊は、前記一般式（１）中で二重結合にて窒素原子と連結する部位を表し、Ｘはそれぞれ独立に、−ＣＲ^１１Ｒ^１２−、−ＣＯ−、−ＣＳ−、−ＮＲ^１３−、−Ｓ−、−ＳＯ_２−、−Ｏ−、または−ＰＲ^１４−を表し、Ｒ^１１〜Ｒ^１４およびＲ^２１〜Ｒ^７８は、それぞれ独立に、水素原子、シアノ基、ニトロ基、−ＯＲ^１５、−ＣＯＯＲ^１５、−ＣＯ−Ｒ^１５、−ＳＲ^１５、ハロゲン原子、無置換若しくは置換基を有している炭素原子数１〜２０の炭化水素基、または、無置換若しくは置換基を有している炭素原子数２〜２０の複素環基を表し、Ｒ^１５は、無置換若しくは置換基を有している炭素原子数１〜２０の炭化水素基、または、無置換若しくは置換基を有している炭素原子数２〜２０の複素環基を表す。） That is, the photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) a photoinitiator and (B) a curable resin.
As the (A) photoinitiator, the following general formula (1),

(In General Formula (1), Ring A ¹ is any one of the following partial structural formulas (1-1) to (1-10), and R ¹ and R ² are each independently a hydrogen atom, A substituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a ring containing nitrogen atoms formed by connecting R ¹ and R ² to each other, and the ring is condensed with a benzene ring; It may be cyclic.) It contains at least 1 type of compound represented by this.

(Wherein, * represents a site connecting to the nitrogen atom at the double bond in the formula (1), X is ^{independently, -CR 11 R 12 -, -} CO -, - CS-, ^{-NR 13 -, - S -,} - SO 2 -, - O-, or ^{-PR 14} - ^represents, R 11 ^{to R 14} and ^R 21 ^{to R 78} each independently represent a hydrogen atom, a cyano group, a nitro ^{group, -OR 15, -COOR 15, -CO} -R 15, -SR 15, halogen atom, unsubstituted or has a substituent hydrocarbon group having 1 to 20 carbon atoms or, an unsubstituted or substituted Represents a heterocyclic group having 2 to 20 carbon atoms having a group, and R ¹⁵ is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted group. Represents a C2-C20 heterocyclic group having a group.)

  In the photosensitive resin composition of this invention, it is preferable to contain (C) alkali developable resin.

  The cured product of the present invention is characterized in that the photosensitive resin composition of the present invention is irradiated with energy rays.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition using the compound which has the outstanding base generating ability, its hardened | cured material, and the novel compound which has the outstanding base generating ability used for this can be provided. Moreover, since the novel compound of the present invention has excellent thermal stability, it is suitable for the curing process of the photosensitive resin composition.

First, the photosensitive resin composition of the present invention will be described.
The photosensitive resin composition of the present invention comprises (A) a photoinitiator (hereinafter also referred to as “component (A)”), (B) a curable resin (hereinafter also referred to as “component (B)”), The (A) photoinitiator contains at least one compound represented by the above general formula (1). Hereinafter, each component of the photosensitive resin composition of the present invention will be described in detail.

で表される構造を有しており、一般式（１）中の環Ａ^１は、炭素原子、窒素原子、硫黄原子、酸素原子およびリン原子から任意に構成される５員〜８員の環である。この５員〜８員の環には他の環が縮環していてもよく、また、置換基を有していてもよい。一般式（１）中のＲ^１およびＲ^２は、それぞれ独立に、水素原子、無置換若しくは置換基を有している炭素原子数１〜２０の炭化水素基、またはＲ^１およびＲ^２が、互いに連結して形成する窒素原子を含む環であり、この環にはベンゼン環環が縮環していてもよい。 <(A) Photoinitiator>
The photoinitiator (A) according to the present invention has the following general formula (1),

The ring A ¹ in the general formula (1) is a 5- to 8-membered ring arbitrarily composed of a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom, and a phosphorus atom. It is. This 5-membered to 8-membered ring may be condensed with another ring, or may have a substituent. R ¹ and R ² in the general formula (1) are each independently a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ² are It is a ring containing nitrogen atoms that are connected to each other, and this ring may be condensed with a benzene ring.

The 5-membered to 8-membered ring in the general formula (1) is not particularly limited, but has 0 to 2 nitrogen atoms, sulfur atoms, oxygen atoms and phosphorus atoms, and the others are 5 to 8 members composed of carbon atoms. Those having the ring are preferred. In addition, a 5- to 8-membered ring having other rings condensed to 2- to 4-rings is preferable. The condensed ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring, a naphthalene ring, or a phenanthrene ring. Preferable specific examples of the ring A ¹ which has been condensed into 2 to 4 rings include the following partial structural formulas (1-1) to (1-10).

Where * in the formula (1-1) to (1-10), in the general formula (1) represents a site connecting to the nitrogen atom at the double bond, X is independently, ^{-CR 11} R ¹² −, —CO—, —CS—, —NR ¹³ —, —S—, —SO ₂ —, —O—, or —PR ¹⁴ — is represented. R ^{11 to} R ¹⁴ and R ^{21 to} R ⁷⁸ are each independently a hydrogen atom, a cyano group, a nitro group, —OR ¹⁵ , —COOR ¹⁵ , —CO—R ¹⁵ , —SR ¹⁵ , a halogen atom, unsubstituted or It represents a hydrocarbon group having 1 to 20 carbon atoms having a substituent or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms. R ¹⁵ represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms. Represent.

In the partial structural formulas (1-1) to (1-10), as the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{11 to} R ¹⁴ , R ^{21 to} R ⁷⁸ and R ¹⁵ , an alkyl group, Examples thereof include aliphatic hydrocarbon groups such as alkenyl groups and alkynyl groups, alicyclic hydrocarbon groups such as cycloalkyl groups, and aromatic hydrocarbon groups such as aryl groups and arylalkyl groups. As the hydrocarbon group, those having 1 to 10 carbon atoms are preferable.

  Specific examples of the unsubstituted hydrocarbon group include, for example, methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, hexyl, heptyl, isoheptyl, t -Heptyl, n-octyl, isooctyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, Aliphatic hydrocarbons such as cyclodecyl; aromatic hydrocarbons such as phenyl and naphthyl; benzyl, 2-phenylethane-1-yl, 3-phenylpropan-1-yl, 1-naphthylmethyl, 2-naphthylmethyl, etc. Alkyl aromatic hydrocarbons linked by a chain.

The alkyl chain of the hydrocarbon group is —O—, —COO—, —OCO—, —CO—, —CS—, —S—, —SO—, —SO ₂ —, —NR ¹⁶ —, —NR ^16. It may be interrupted by —CO—, —CO—NR ¹⁶ —, —NR ¹⁶ —COO—, —OCO—NR ¹⁶ — or —SiR ¹⁷ R ¹⁸ —. The hydrogen atom in the hydrocarbon group is a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom, cyano group, nitro group, hydroxyl group, thiol group, amino group (—NH ₂ ), carboxyl group (—COOH). ) Or a sulfino group (—SO ₂ H). R ^{16 to} R ¹⁸ are the same as a hydrogen atom or a hydrocarbon group not having the above substituent. The interruption and substitution of the alkyl chain of the hydrocarbon group may be combined.

Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ^{11 to} R ^14, R ^{21 to} R ⁷⁸ , and R ^{15 in the} partial structural formulas (1-1) to (1-10) include an alicyclic group. A heterocyclic group and an aromatic heterocyclic group are mentioned. Specific examples of the unsubstituted heterocyclic group include tetrahydrofuran, dioxolanyl, tetrahydropyranyl, morpholylfuran, thiophene, methylthiophene, hexylthiophene, benzothiophene, pyrrole, pyrrolidine, Examples include imidazole group, imidazolidine group, pyrazole group, pyrazolidine group, piperidine group and piperazine group. Examples of the heterocyclic group having a substituent include hydrocarbon groups having 1 to 20 carbon atoms represented by R ^{11 to} R ¹⁴ , R ^{21 to} R ^78, and R ^{15 in} the above heterocyclic group. The heterocyclic group which the same thing as the hydrocarbon group which did not have a substituent demonstrated in 1 was substituted is mentioned.

The alkylene moiety in these heterocyclic groups and the bond between the heterocyclic ring and the alkyl group are -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-,- May be interrupted by SO ₂ —, —NR ¹⁶ —, —NR ¹⁶ —CO—, —CO—NR ¹⁶ —, —NR ¹⁶ —COO—, —OCO—NR ¹⁶ — or —SiR ¹⁷ R ¹⁸ —. . However, these discontinuing divalent groups are not adjacent to each other. R ^{16 to} R ¹⁸ are the same as the hydrocarbon groups having no substituent described in the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{11 to} R ¹⁴ , R ^{21 to} R ⁷⁸ and R ^15. is there.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² in the general formula (1) has a substituent or is unsubstituted, and R ^{11 to} R ¹⁴ and R ^{21 to} R ⁷⁸ and the same groups as those described for R ¹⁵ are represented.

In the case where R ¹ and R ² are a ring containing a nitrogen atom formed by connecting to each other, examples of the other atoms constituting the ring include a carbon atom and an oxygen atom, and the ring is a 5-membered or 6-membered ring. Some are preferred. Preferred examples of the ring formed by linking R ¹ and R ² include a pyrrole group, a pyrrolidine group, an imidazole group, an imidazolidine group, a pyrazole group, and a pyrazolidine group as a group including a bonded nitrogen atom. , A piperidine group, a piperazine group, and the like, and a pyrrolidine group, an imidazole group, a piperidine group, and a piperazine group are preferable. In these rings, a benzene ring may be condensed or may have a substituent. Examples of the substituent include an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, and t-butyl group, methylol group, ethylol group, propylol group, and butyrol. And a hydroxyalkyl group such as a group.

  In the compound represented by the general formula (1), there are isomers as shown below, but they are the same in the effects of the present invention, and any of the compounds can be used similarly.

The compound represented by the general formula (1) is a compound in which R ¹ or R ² is a phenyl group from the viewpoint of excellent curability of the photosensitive resin composition; neither of R ¹ and R ² is a hydrogen atom Compound: A compound in which R ¹ and R ² are connected to each other to form a ring is preferable, and a compound in which R ¹ and R ² are connected to each other to form a pyrrolidine ring, an imidazole ring, a piperidine ring, or a piperazine ring More preferred.

  Specific examples of the compound represented by the general formula (1) include the following compound Nos. 1-No. 18 is mentioned. However, the compound represented by the general formula (1) is not limited at all by the following compounds.

Although the compound represented by General formula (1) is not specifically limited, For example, it can manufacture by the method of the following reaction formula. That is, the Lawson reagent is reacted with the ketone body (2) to synthesize the thioketone body (3), and further hydroxylamine is reacted under basic conditions to synthesize the oxime body (4). The oxime ester (1) can be synthesized by reacting the oxime (4) with 4-nitrophenyl chloroformate under basic conditions and then reacting with the amine (5). Incidentally, in the following reaction ^formula, A ^1, R 1, ^{R 2} are the same as in the general formula (1)

  In the photosensitive resin composition of the present invention, the component (A) contains at least one compound represented by the general formula (1). (A) Content of the compound of this invention in a component becomes like this. Preferably it is 1-100 mass%, More preferably, it is 50-100 mass%. (A) Other components of the photoinitiator are not particularly limited as long as they can function as a photoinitiator, and known photoinitiators can be used.

  In the photosensitive resin composition of this invention, content of (A) component becomes like this. Preferably it is 1-20 mass parts with respect to 100 mass parts of (B) component, More preferably, it is 1-10 mass parts. When the content of the component (A) is less than 1 part by mass, poor curing due to insufficient sensitivity may occur, and when it exceeds 20 parts by mass, volatiles may be increased during light irradiation or heating. is there.

<(B) curable resin>
The component (B) used in the present invention represents a resin whose curing temperature is lowered by using an anion polymerizable functional group or base as a catalyst, and is a curable resin that is polymerized and cured by irradiation with energy rays such as ultraviolet rays. Alternatively, it is a curable resin whose curing temperature is lowered. The anionic polymerizable functional group means a functional group that can be polymerized by a base generated from a photobase generator by an active energy ray such as ultraviolet rays. For example, an epoxy group, an episulfide group, a cyclic monomer (σ-valerolactone, ε-caprolactam) and the like, and as a resin whose curing temperature is lowered by using a base as a catalyst, urethane bond formation reaction by isocyanate and alcohol, epoxy and hydroxyl group addition reaction, epoxy and carboxylic acid group addition reaction, epoxy and Examples include those utilizing thiol group addition reaction, (meth) acrylic group Michael addition reaction, polyamic acid dehydration condensation reaction, and the like. Examples of the component (B) include epoxy resins, oxetane resins, polyamide resins, polyurethane resins, nylon resins, and polyester resins. These resins may be used alone or in combination of two or more. Among these, an epoxy resin is preferable because the reaction proceeds quickly and the adhesiveness is good.

  Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol) , Ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4′-dihydroxybenzophenone, isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4 -Bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thio Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as sphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol, Polyglycidyl ethers of polyhydric alcohols such as butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, Succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, seba Aliphatic acids such as acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid and endomethylenetetrahydrophthalic acid, aromatic Or glycidyl esters of alicyclic polybasic acids, and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, Epoxy compounds having a glycidylamino group such as diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6 -Methyl Epoxidized products of cyclic olefin compounds such as cyclohexylmethyl-6-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized acrylonitrile-butadiene copolymer, epoxidized styrene Examples include epoxidized conjugated diene polymers such as butadiene copolymer and heterocyclic compounds such as triglycidyl isocyanurate. In addition, these epoxy resins may be those internally crosslinked by a prepolymer of a terminal isocyanate or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). .

  Among the epoxy resins, those having a glycidyl group are preferable from the viewpoint of excellent curability, and those having a bi- or higher functional glycidyl group are more preferable. These may be used alone or in combination of two or more.

  The oxetane resin is a compound having a 4-membered ring ether (oxetanyl group) in the molecule. Specific examples include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, phenol novolak oxetane, 1,3- Bis [(3-ethyloxetane-3-yl) methoxy] benzene, oxetanylsilsesquioxane, oxetanyl silicate, and the like. These may be used alone or in combination of two or more.

  As the polyamide resin, as the acid dianhydride, ethylenetetracarboxylic dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Examples of anhydrides and diamines include (o-, m- or p-) phenylenediamine, (3,3′- or 4,4 ′-) diaminodiphenyl ether, diaminobenzophenone, (3,3′- or 4,4). Examples include resins made from '-) diaminodiphenylmethane or the like. These may be used alone or in combination of two or more.

  As a polyurethane resin, as diisocyanate, polyfunctional isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate, and polyols (polyfunctional alcohol) such as polyether polyol, polyester polyol, and polycarbonate polyol are used as raw materials. Examples thereof include resins. Examples of nylon resins include resins made from cyclic monomers such as ε-caprolactam and lauryl lactam. Examples of the polyester resin include resins made from cyclic monomers such as δ-valerolactone and β-propiolactone. These may be used alone or in combination of two or more.

<(C) Alkali developable resin>
The photosensitive resin composition of the present invention can use (C) an alkali-developable resin (hereinafter also referred to as “component (C)”) for the purpose of patterning using an alkaline solution. Component (C) is a resin that contains one or more functional groups among phenolic hydroxyl groups, thiol groups, and carboxyl groups and that can be developed with an alkaline solution, preferably a compound having two or more phenolic hydroxyl groups, carboxyl Examples thereof include a group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. These resins may be used alone or in combination of two or more.

  Examples of the compound having two or more phenolic hydroxyl groups include phenol novolac resin, alkylphenol volac resin, bisphenol A type novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinylphenols, bisphenol F Bisphenol S-type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, and the like. These may be used alone or in combination of two or more.

  In addition, as a phenol resin, a compound having a biphenyl skeleton or a phenylene skeleton, or both, and as a phenolic hydroxyl group-containing compound, phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4- Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol You may use the phenol resin which synthesize | combined using these and which have various frame | skeletons. These may be used alone or in combination of two or more.

  As the carboxyl group-containing resin, a known resin containing a carboxyl group can be used. Due to the presence of the carboxyl group, the resin composition can be made alkali developable. In addition to the carboxyl group, a compound having an ethylenically unsaturated bond in the molecule may be used, but in the present invention, for example, the carboxyl group-containing resin does not have an ethylenically unsaturated double bond. It is preferable to use only a carboxyl group-containing resin. The carboxyl group-containing resin may also be used alone or in combination of two or more.

  Specific examples of the carboxyl group-containing resin that can be used in the present invention include the compounds listed below (any of oligomers and polymers).

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. The lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound.

(5) During the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing urethane resin.

(6) During the synthesis of the resin of the above (2) or (4), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

(7) The polyfunctional epoxy resin exemplified as the component (B) is reacted with an unsaturated monocarboxylic acid such as (meth) acrylic acid, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride is added to the hydroxyl group present in the side chain. A carboxyl group-containing resin to which a dibasic acid anhydride such as an acid is added.

(8) Saturated monocarboxylic acid is reacted with the polyfunctional epoxy resin exemplified as the component (B), and the hydroxyl group present in the side chain is dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A carboxyl group-containing resin to which is added.

(9) A carboxyl obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the resulting hydroxyl group Group-containing resin.

(10) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin exemplified as the component (B) with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

(11) Non-photosensitive carboxyl obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide. Group-containing resin.

(12) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is allowed to react with a saturated monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a basic acid anhydride.

(13) Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a product.

(14) A reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, with a saturated monocarboxylic acid. A carboxyl group-containing resin obtained by reacting with a polybasic acid anhydride.

(15) A carboxyl group obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. Containing resin.

(16) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a reaction product with a polybasic acid anhydride.

(17) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and a saturated monocarboxylic acid React with acid and react with polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid etc. to the alcoholic hydroxyl group of the resulting reaction product Carboxyl group-containing resin obtained by making it.

(18) An epoxy compound having a plurality of epoxy groups in one molecule is reacted with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol; Carboxyl groups obtained by reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid with the alcoholic hydroxyl group of the obtained reaction product Containing resin.

(19) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as an acid.

(20) One epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (19) above A carboxyl group-containing resin formed by adding a group-containing compound.

  Examples of the compound having a thiol group include trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, trimethylolpropane tris. Thioglycolate, pentaerythritol tetrakisthioglycolate, di (2-mercaptoethyl) ether, 1,4-butanedithiol, 1,3,5-trimercaptomethylbenzene, 1,3,5-trimercaptomethyl-2 , 4,6-trimethylbenzene, terminal thiol group-containing polyether, terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound and hydrogen sulfide, reaction of polythiol compound and epoxy compound Thiol compounds, and the like with terminal thiol groups to be. These may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, the blending amount of the component (C) is preferably 50 to 1000 parts by weight with respect to 100 parts by weight of the component (B). In some cases, it may become insoluble in the solution, and when it is more than 1000 parts by mass, curing failure may occur during irradiation with energy rays.

<(D) Additive>
In the photosensitive resin composition of the present invention, as optional components, (D) additives (hereinafter referred to as “(D)” such as inorganic compounds, coloring materials, latent epoxy curing agents, chain transfer agents, sensitizers, and solvents. Also referred to as “component”).

  Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay mineral, miloli blue, calcium carbonate, carbonic acid Magnesium, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold , Silver, copper and the like. These inorganic compounds are used as, for example, a filler, an antireflection agent, a conductive material, a stabilizer, a flame retardant, a mechanical strength improver, a special wavelength absorber, and an ink generating agent. These inorganic compounds may be used alone or in combination of two or more.

  Examples of the color material include pigments, dyes, and natural pigments. These color materials can be used alone or in admixture of two or more.

Examples of pigments include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; Perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acids; metal complex compounds of azo dyes and cyanine dyes; lake pigments; Or carbon black such as acetylene black, ketjen black or lamp black; Prepared by coating or coating with an epoxy resin, carbon black previously dispersed with a resin in a solvent and adsorbed with 20 to 200 mg / g of resin, an acid or alkaline surface treated carbon black, average Carbon black having a particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a carbon black having a total oxygen amount calculated from CO and CO ₂ in a volatile content at 950 ° C. of 9 mg or more per 100 m ^{2 of} surface area; Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series, F Erocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black, amber, etc. Organic or inorganic pigments can be used. These pigments may be used alone or in combination of two or more.

  Commercially available pigments can also be used as the pigment. For example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 9 , 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, and the like.

  As dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, Examples include dyes such as cyanine dyes, and a plurality of these may be used in combination.

  Examples of latent epoxy curing agents include dicyandiamide, modified polyamines, hydrazides, 4,4′-diaminodiphenyl sulfone, boron trifluoride amine complex salts, imidazoles, guanamines, ureas, and melamine. May be used in combination.

  As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compound, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, aliphatic polyfunctional thiol compounds such as the following compound D1 And Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko KK.

  As the solvent, usually, a solvent capable of dissolving or dispersing each of the above components (component (A), component (B) and component (C)), for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl Ketones such as isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; acetic acid Ester solvents such as methyl, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Cellosolve solvents such as methanol; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl Ether ester solvents such as ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; BTX solvents such as benzene, toluene, xylene; hexane, heptane, octane, cyclohexane, etc. Aliphatic hydrocarbon solvents; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Paraffin solvents such as Besso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatics such as chlorobenzene Carbitol solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylpyrrolidone; dimethyl sulfoxide; These solvents can be used alone or as a mixed solvent of two or more. Among these, ketones or ether ester solvents, in particular, propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone are preferably used from the viewpoints of alkali developability, patterning property, film forming property, and solubility.

  In the photosensitive resin composition of the present invention, the content of the solvent is not particularly limited, each component is uniformly dispersed or dissolved, and the photosensitive resin composition of the present invention is in a liquid or paste form suitable for each application. In general, it is preferable that the solvent is contained in a range in which the solid content (all components other than the solvent) in the photosensitive resin composition of the present invention is 10 to 90% by mass.

  In the photosensitive resin composition of the present invention, a surfactant, a silane coupling agent, a melamine compound and the like can be further used in combination.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; higher amines Cationic surfactants such as halogenates and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; silicone surfactants Surfactants such as agents can be used, and these may be used in combination. These surfactants may be used alone or in combination of two or more.

  As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, silanes having an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, and KBE-403. A coupling agent is preferably used.

As the melamine compound, all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea ( Examples include compounds in which at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.

  Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable from the viewpoints of solubility in a solvent and difficulty in crystal precipitation from the photosensitive resin composition.

  In the photosensitive resin composition of the present invention, the amount of optional components other than the components (A), (B) and (C) (excluding inorganic compounds, coloring materials, and solvents) is the purpose of use. Although it is suitably selected according to the above and is not particularly limited, it is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the component (B).

Next, the cured product of the present invention will be described.
The cured product of the present invention is obtained by irradiating the photosensitive resin composition of the present invention with energy rays. For example, (1) a step of forming a coating film of the photosensitive resin composition of the present invention on a substrate, (2) a step of irradiating the coating film with energy rays (light) through a mask having a predetermined pattern shape (3) A baking process after exposure, (4) a process of developing the film after exposure, and (5) a process of heating the film after development, a patterned cured product can be obtained.

  (1) As a step of forming a coating film of the photosensitive resin composition of the present invention on a substrate, a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, It can be applied to a supporting substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, and plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method. In addition, when the photosensitive resin composition contains a solvent, it is preferable to remove a solvent using a hotplate, oven, etc. after coating.

  (2) In the step of irradiating the coating film with energy rays (light) through a mask having a predetermined pattern shape, the light source of the energy rays used is an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a medium pressure mercury lamp. Electromagnetic waves having a wavelength of 200 to 700 nm obtained from low pressure mercury lamp, mercury vapor arc lamp, xenon arc lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc. High energy rays such as energy, electron beam, X-ray, and radiation can be used, but preferably an ultra-high pressure mercury lamp, mercury vapor arc lamp, carbon arc lamp, xenon arc that emits light having a wavelength of 300 to 450 nm. A lamp or the like is used.

  Further, by using laser light as an exposure light source, a laser direct drawing method that directly forms an image from digital information such as a computer can be used without using a mask. The laser direct writing method is useful because it can improve not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used. Lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium neon lasers, krypton ion lasers, various semiconductor lasers, YAG lasers, and the like that emit light in the visible to infrared region can also be used. When these laser beams are used, a sensitizing dye that absorbs the visible to infrared region is preferably added.

  (3) In the baking step after exposure, heating at about 40 to 150 ° C. is preferable in terms of the curing rate after irradiation with the energy beam.

  (4) In the step of developing the film after exposure, the alkaline developer is a mixture of an aqueous solution of an alkaline compound and, if necessary, a water-soluble organic solvent, a surfactant or the like. Examples of the alkaline compound in the alkaline developer include inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, and triethanolamine. , Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, etc. Examples include cyclic tertiary amines, amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and ammonium compounds. In the patterning of the photosensitive resin composition of the present invention, not only an alkali developer but also an organic solvent can be used, and examples of the organic solvent used include cyclopentanone.

  (5) The step of heating the film after development is not an essential step, but is preferable because the hardness of the cured film is further improved. Post bake is preferably performed at 160 ° C. to 250 ° C. for 5 minutes to 3 hours using a heating device such as a hot plate or oven.

  The photosensitive resin composition of the present invention comprises: a photoresist for electronics; an electroplating resist; an etching resist; a dry film; a solder resist; a color filter for various display applications; a plasma display panel; Resist for forming their structures in the manufacturing process of display devices and LCDs; Composition for encapsulating electrical and electronic parts; Solder resist; Magnetic recording material; Micro mechanical parts; Waveguide; Optical switch; Masks; Etching masks; Color test systems; Glass fiber cable coatings; Screen printing stencils; Materials for producing three-dimensional objects by stereolithography; Microelectronic circuits; Photoresist materials for printed wiring boards; UV and visible laser direct Photoresist materials for image systems; Can be used in various applications such as a photoresist material or a protective film for use in the dielectric layer formed in a sequential lamination of lint circuit board, there is no particular limitation on the application.

  The photosensitive resin composition of the present invention to which a color material is added is suitably used as a resist constituting each pixel such as RGB in a color filter and a black matrix resist forming a partition of each pixel. Furthermore, in the case of a black matrix resist to which an ink repellent agent is added, it is preferably used for a partition for an ink jet color filter having a profile angle of 50 ° or more. As the ink repellent agent, a fluorosurfactant and a composition containing a fluorosurfactant are preferably used.

  When used as a partition for an ink jet type color filter, the partition formed from the photosensitive resin composition of the present invention partitions the transferred body, and droplets are applied to the recessed portions on the partitioned transferred body by the inkjet method. Thus, an optical element is manufactured by a method of forming an image region. At this time, it is preferable that the droplets contain a colorant and the image area is colored. In this case, the optical element produced by the manufacturing method described above is formed from a plurality of colored areas on the substrate. And at least a partition that separates each colored region of the pixel group.

  The photosensitive resin composition of the present invention can also be used as a protective film or insulating film composition. In this case, an ultraviolet absorber, an alkylation-modified melamine and / or an acrylic-modified melamine, a mono- or bifunctional (meth) acrylate monomer containing an alcoholic hydroxyl group in the molecule, and / or silica sol can be contained.

  The insulating film is used for the insulating resin layer in a laminate in which an insulating resin layer is provided on a peelable support substrate, and the laminate can be developed with an aqueous alkaline solution. The film thickness is preferably 10 to 100 μm.

  The photosensitive resin composition of the present invention can be used as a photosensitive paste composition by containing an inorganic compound. The photosensitive paste composition can be used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.

Next, the novel compound represented by the general formula (1 ′) will be described in detail.
In general formula (1 ′), ring A ¹ is a 5-membered to 8-membered ring arbitrarily composed of a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom and a phosphorus atom, and is a 5-membered to 8-membered ring. The other ring may be condensed and may have a substituent. R ¹ and R ² are each independently a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or nitrogen formed by R ¹ and R ² being linked to each other A ring containing atoms. When the atom constituting the 5- to 8-membered ring represented by the ring A ¹ does not contain a nitrogen atom, R ¹ and R ² are rings formed by being connected to each other, and this ring is a nitrogen atom, an oxygen atom And a carbon atom, and a benzene ring may be condensed to this ring. In addition, a 5- to 8-membered ring having other rings condensed to 2- to 4-rings is preferable. The condensed ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring, a naphthalene ring, or a phenanthrene ring. Preferable specific examples of the ring A ¹ that has been condensed into 2 to 4 rings include the partial structural formulas (1-1) to (1-10) described above.

  The novel compound of the present invention has high chemical stability and excellent thermal stability. In addition to being used as the component (A) of the above-described photosensitive resin composition, the novel compound can be used as a chemically amplified resist. Can be used.

  EXAMPLES Hereinafter, although an Example and an experiment example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples etc.

[Example 1-1] Compound No. 1 Synthesis of 1 A solution of benzo [cd] indole-2 (1H) -one 5.0 g (30 mmol), Lawesson's reagent 3.3 g (8 mmol) and toluene 50 mL was stirred at 100 ° C. for 1.5 hours. After cooling, water was added to separate the oil and water, and the oil layer was washed with an aqueous sodium bicarbonate solution. The oil layer was dried over anhydrous magnesium sulfate and then desolvated under reduced pressure to obtain 7.9 g of a mixture of a thioamide and a Lawson reagent decomposition product.

  A solution of 7.9 g of the obtained mixture, 3.1 g (45 mmol) of hydroxylamine hydrochloride, 4.6 g (45 mmol) of triethylamine and 50 mL of ethanol was stirred at reflux temperature for 3.5 hours. After cooling, 200 mL of water was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to obtain 4.9 g (yield 90%) of the oxime.

To a solution of 2.0 g (11 mmol) of the obtained oxime, 2.2 g (22 mmol) of triethylamine and 10 mL of chloroform, a solution of 2.4 g (12 mmol) of 4-nitrophenyl chloroformate and 3 mL of chloroform was added dropwise under ice water cooling. After stirring for 1.5 hours, 1.0 g (12 mmol) of piperidine was added dropwise. After stirring at room temperature for 4 hours, water was added to separate the oil and water, and the oil layer was washed with water. The oily layer was dried over anhydrous magnesium sulfate and then desolvated under reduced pressure, and the resulting oily product was purified by silica gel column chromatography (toluene / ethyl acetate = 5: 1). 34%). It was confirmed by ¹ H-NMR and IR spectrum that the obtained compound was the target product. The results are shown in Table 2 and Table 3.

[Examples 1-2 to 1-6] Compound Nos. 2-5 and no. In the same manner as in Example 1, compound No. 9 was synthesized. 2-5 and no. 9 was synthesized. Physical property data etc. are shown in Tables 1-3.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）

¹ H-NMR (CDCl ₃ )

  In Table 2, a proton number of 0.5H means 1H of either isomer, and 1.5H means 3H of either isomer.

ＩＲスペクトル（ＡＴＲ）

IR spectrum (ATR)

[Examples 2-1 and 2-2 and Comparative Example 2-1] Evaluation of Compound Remaining Ratio As Examples 2-1 and 2-2 and Comparative Example 2-1, compound Nos. The residual ratio of the compound was evaluated using 4, 5 and the comparative compound. First, compound no. Each of 4, 5 and the comparative compound was dissolved in a solvent of acetic acid / water = 9: 1 so as to be 0.1% by mass. The resulting solution was warmed for 3 hours with stirring so that the temperature reached 80 ° C. The residual ratio of the compound after 3 hours was calculated with the initial value after dissolution (0 hour). In calculating the compound residual ratio, high performance liquid chromatography (HPLC) was used for the analysis. The results obtained are shown in Table 4 below.

[Examples 3-1 to 3-6] Preparation examples and evaluation examples 1 of photosensitive resin compositions
As component (A), 5 parts by mass of the compounds shown in Table 5 below, as component (B), 52 parts by mass of EP-4901 (manufactured by ADEKA, bisphenol F-type glycidyl ether), and (D) as an additive component , Karenz MT BD1 (manufactured by Showa Denko KK, epoxy curing agent) 43 parts by mass were mixed and kneaded in a three-roll mill to obtain a photosensitive resin composition. The obtained photosensitive resin composition was heated at 60 ° C. for 60 minutes after irradiation with UV light by an ultrahigh pressure mercury lamp and irradiation with 200 mJ / cm ² of UV light, and the curing rate was measured. Curing rate after UV light irradiation of 5,000 mJ / cm ^2, (peak intensity of 3,450cm ^-1) in FT-IR of when cured 60 minutes at 120 ° C. / (peak intensity of 1,510Cm ^-1 ) Was determined as a relative value with a curing rate of 100%. The results are shown in [Table 5] below.

[Examples 4-1 to 4-12] Preparation examples and evaluation examples 2 of photosensitive resin compositions
After blending in the composition ratios shown in Tables 6 and 7 below, the photosensitive resin composition of the present invention was prepared by kneading with a three-roll mill. The obtained photosensitive resin composition was apply | coated to the glass substrate (it adjusted so that the film thickness after a prebaking might be 6 micrometers), and was dried for 2 minutes with a 90 degreeC hotplate. After irradiation with 250 mJ / cm ^{2 with a} high-pressure mercury lamp (manufactured by HOYA CANDEO OPTRONICS CORPORATION, irradiation illuminance 20 mW / cm ² ), the mixture was heated at 130 ° C. for 50 minutes. Then, it developed using the following developing solution. From the change in film thickness before and after development in the irradiated part, the development resistance of the irradiated part (cured part) was evaluated, and the developability of the non-irradiated part was evaluated. The results are shown in Tables 6 and 7.

<Curing property>
This represents the film thickness after development when the film thickness before development is 100. The closer to 100, the higher the curability and the better the development resistance. The developer used for the evaluation was an alkaline aqueous solution (hereinafter referred to as a TMAH developer) prepared so that tetramethylammonium hydroxide (TMAH) containing 5% by mass of ethanolamine was 3% by mass.

<Developability>
Developed with cyclopentanone (organic solvent), developed with TMAH developer, ◎, developed with cyclopentanone, and developed with TMAH developer, ◯ The case where development was impossible even with cyclopentanone was marked as x.

<(A) component>
No. 1: Compound No. Compound No. 1 2: Compound No. Compound No. 2 3: Compound No. Compound No. 3 4: Compound No. Compound No. 4 5: Compound No. Compound 5 <(B) component>
EPPN-201: phenol novolac type epoxy resin, epoxy equivalent 193 g / eq. Manufactured by Nippon Kayaku Co., Ltd. G-01100: Epoxy group-containing acrylic polymer, epoxy equivalent 170 g / eq. , Mw = 12,000, manufactured by NOF Corporation (component (C))
TRR-5010G: Cresol novolac type phenol resin, hydroxyl group equivalent of 120 g / eq. , Mw = 8,000, manufactured by Asahi Organic Materials Co., Ltd. GDP-6095LR: dicyclopentadiene-modified phenol resin, hydroxyl group equivalent 168-171 g / eq. , Mw = 443, made by Gunei Chemical Co., Ltd. Copolymer 1: styrene-methyl methacrylate copolymer, styrene / methyl methacrylate = 80/20, Mw = 8,000, acid value = 14 mgHOH / g
<Non-alkali developable resin>
Non-alkali developable phenol novolac type phenol resin, hydroxyl group equivalent 0 g / eq. , Mw = 14,000

From the above, it is clear that the photosensitive resin composition of the present invention has excellent curability and developability, and the compound of the present invention used for this has excellent base generating ability. is there.

Claims (3)

In the photosensitive resin composition containing (A) photoinitiator and (B) curable resin,
As the (A) photoinitiator, the following general formula (1),

(In General Formula (1), Ring A ¹ is any one of the following partial structural formulas (1-1) to (1-10), and R ¹ and R ² are each independently a hydrogen atom or unsubstituted. Or a hydrocarbon group having 1 to 20 carbon atoms having a substituent, or a ring containing nitrogen atoms formed by connecting R ¹ and R ² to each other, and a benzene ring condensed to the ring A photosensitive resin composition comprising at least one compound represented by formula (1):

(Wherein, * represents a site connecting to the nitrogen atom at the double bond in the formula (1), X is ^{independently, -CR 11 R 12 -, -} CO -, - CS-, ^{-NR 13 -, - S -,} - SO 2 -, - O-, or ^{-PR 14} - ^represents, R 11 ^{to R 14} and ^R 21 ^{to R 78} each independently represent a hydrogen atom, a cyano group, a nitro ^{group, -OR 15, -COOR 15, -CO} -R 15, -SR 15, halogen atom, unsubstituted or has a substituent hydrocarbon group having 1 to 20 carbon atoms or, an unsubstituted or substituted Represents a heterocyclic group having 2 to 20 carbon atoms having a group, and R ¹⁵ is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted group. Represents a C2-C20 heterocyclic group having a group.)   (C) The photosensitive resin composition of Claim 1 containing alkali developable resin.   A cured product obtained by irradiating the photosensitive resin composition according to claim 1 or 2 with energy rays.