JP2019116479A - Novel compound - Google Patents

Abstract

To provide a novel compound having excellent base generation performance.SOLUTION: There is provided a novel compound represented by the following general formula (1'), wherein a ring Ais one of following partial structural formulae (1-1) to (1-10), Rand Rare each independently a hydrogen atom, an unsubstituted or substituted hydrocarbon group with 1 to 20 carbon atoms, or Rand Rare connected each other to form a ring containing a nitrogen atom, when an atom constituting a 5- to 8-membered ring represented by the ring Acontains no nitrogen atom, Rand Rare the ring formed by connecting each other, the ring is formed optionally selected from a nitrogen atom, an oxygen atom, and a carbon atom, and a benzene ring may be condensed to the ring.SELECTED DRAWING: None

Description

  The present invention relates to a novel compound, and more particularly, to a novel compound having excellent base generation ability.

  In general, a photosensitive resin composition is one obtained by adding a photoinitiator to a photosensitive resin, and can be polymerized and cured or developed by energy beam (light) irradiation, so a photocurable ink, a photosensitive printing plate It is used in various photoresists, photocurable adhesives and the like.

  Photoinitiators are classified into photo radical generators, photo acid generators, and photo base generators according to the difference in active species generated by energy beam (light) irradiation. The photo radical generator has advantages such as fast curing speed and no remaining active species after curing. However, since curing inhibition occurs due to oxygen, it has the disadvantage that a layer or the like that blocks oxygen must be provided when curing a thin film. The photo acid generator has the advantage of not being inhibited by oxygen, but has the disadvantage of causing corrosion of the metal substrate due to the remaining of the acid of the active species, or modifying the resin after curing. Have. On the other hand, photobase generators are attracting attention because they are less likely to cause problems such as curing inhibition by oxygen and corrosion by residual active species. However, they generally have a problem of low sensitivity (low curing property) as compared with photoacid generators. So far, various proposals have been made for photobase generators, and as prior art, for example, Patent Documents 1 to 3 and the like can be mentioned.

Japanese Patent Application Publication No. 2001-513765 International Publication WO 2010/064631 International Publication WO 2010/064623

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

  Therefore, an object of the present invention is to provide a novel compound having an excellent ability to generate a base.

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, a compound having a specific structure has high base generation ability as a photoinitiator, and using the compound as a photobase generator It has been found that the problem can be solved, and the present invention has been completed.

（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、環Ａ^１が表す５員〜８員の環を構成する原子が窒素原子を含まない場合、Ｒ^１およびＲ^２は、互いに連結して形成する環であり、該環は、窒素原子、酸素原子および炭素原子から任意に選ばれて形成され、該環にはベンゼン環が縮環していてもよい。）で表されることを特徴とするものである。 That is, the novel compound of the present invention has the following general formula (1 ′),

(In the general formula (1 ′), ring A ¹ is any of the following partial structural formulas (1-1) to (1-10), and R ¹ and R ² are each independently a hydrogen atom or no atom A substituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a ring containing a nitrogen atom formed by linking R ¹ and R ² to each other, a 5-membered member represented by ring A ¹ When the atoms constituting the 8-membered ring do not contain a nitrogen atom, R ¹ and R ² are rings formed by linking each other, and the ring is optionally selected from a nitrogen atom, an oxygen atom and a carbon atom And the benzene ring may be fused to the ring.

Here, in the formula, * represents a site linked to a nitrogen atom through a double bond in the general formula (1 ′), and X each independently represents —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 no R ¹⁵ represents a substituted or substituted heterocyclic group having 2 to 20 carbon atoms, and R ¹⁵ is a hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or has a substituted group, or A heterocyclic group having 2 to 20 carbon atoms which has a substituted or substituted group It is.

In the novel compound of the present invention, R ¹ and R ² are preferably a ring containing a nitrogen atom formed by linking to each other.

（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、−ＮＲ^１３−を表し、Ｒ^１３は、それぞれ独立に、水素原子、ニトロ基、無置換若しくは置換基を有している炭素原子数１〜２０の炭化水素基を表し、Ｒ^２５〜Ｒ^３０は、それぞれ独立に、水素原子、またはニトロ基を表す。）で表され新規化合物であることが好ましく、この場合、前記無置換若しくは置換基を有している炭素原子数１〜２０の炭化水素基が、炭素原子数１〜２０のアルキル基であることがより好ましい。 Further, in the novel compound of the present invention, ring A ¹ has the following partial structural formula (1-2),

(Wherein, * represents a site linked to a nitrogen atom through a double bond in the general formula (1 ′), X represents —NR ¹³ —, and R ¹³ independently represents a hydrogen atom. , A nitro group, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, and R ^{25 to} R ³⁰ each independently represent a hydrogen atom or a nitro group. Preferred is a novel compound, and in this case, it is more preferred that the above-mentioned unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms is an alkyl group having 1 to 20 carbon atoms. .

（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、−ＣＯ−、−ＣＳ−、−ＮＲ^１３−を表し、Ｒ^１３は、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の炭化水素基を表し、Ｒ^３５〜Ｒ^４０は、水素原子を表す。）で表される新規化合物であることも好ましく、この場合、前記無置換若しくは置換基を有している炭素原子数１〜２０の炭化水素基が、炭素原子数１〜２０のアルキル基であることがより好ましい。 Furthermore, in the novel compound of the present invention, ring A ¹ has the following partial structural formula (1-4),

(Wherein, * represents a site linked to a nitrogen atom by a double bond in the general formula (1 ′), X represents —CO—, —CS—, —NR ¹³ —, R ¹³ Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ^{35 to} R ^{40 each} represent a hydrogen atom. In this case, the unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms is more preferably an alkyl group having 1 to 20 carbon atoms.

（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、−Ｓ−を表し、Ｒ^７１〜Ｒ^７８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の炭化水素基を表す。）で表される新規化合物であることも好ましく、この場合、前記無置換若しくは置換基を有している炭素原子数１〜２０の炭化水素基が、炭素原子数１〜２０のアルキル基であることがより好ましい。 Furthermore, ring A ¹ has the following partial structural formula (1-10),

(Wherein, * represents a site linked to a nitrogen atom by a double bond in the general formula (1 ′), X represents —S—, and R ^{71 to} R ⁷⁸ each independently represent It is also preferable that the compound is a novel compound represented by a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or has a substituent. In this case, it is preferable to have the above-mentioned unsubstituted or substituent. It is more preferable that the said C1-C20 hydrocarbon group is a C1-C20 alkyl group.

  The novel compounds of the present invention are useful for photobase generators.

  According to the present invention, novel compounds having excellent base generation ability can be provided. In addition, the novel compound of the present invention is suitable for the curing process of a photosensitive resin composition because it has excellent thermal stability.

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)") and (B) a curable resin (hereinafter referred to as "component (B)"). And 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 (A) photoinitiator according to the present invention has the following general formula (1),

And the ring A ¹ in the general formula (1) is a 5- to 8-membered ring optionally composed of a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom and a phosphorus atom It is. Another ring may be fused to this 5- or 8-membered ring, and may have a substituent. R ¹ and R ² in the general formula (1) each independently represent 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 formed by being linked to each other, and a benzene ring may be fused to this ring.

The 5- to 8-membered ring in the general formula (1) is not particularly limited, but it has 0 to 2 nitrogen atoms, sulfur atoms, oxygen atoms and phosphorus atoms, and the others are 5 to 8 members consisting of carbon atoms Those which are rings of are preferred. Further, it is preferable that the other ring be condensed to form a 2- to 4-ring ring in a 5- to 8-membered ring. The ring to be fused is preferably an aromatic hydrocarbon ring, more preferably a benzene ring, a naphthalene ring or a phenanthrene ring. The following partial structural formulas (1-1) to (1-10) can be mentioned as preferable specific examples of the ring A ¹ which is condensed to 2 to 4 rings.

Here, * in the formulas (1-1) to (1-10) represents a site connected to a nitrogen atom through a double bond in the general formula (1), and X's each independently represent —CR ^{11 R 12 -, - CO -,} - CS -, - NR 13 -, - S -, - SO 2 -, - O-, or ^{-PR 14} - represents a. 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 This represents a hydrocarbon group having 1 to 20 carbon atoms having a substituent, or a heterocyclic group having 2 to 20 carbon atoms having an unsubstituted or substituted group. R ¹⁵ is a hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or has a substituent, or a heterocyclic group having 2 to 20 carbon atoms which is unsubstituted or has a substituent Represent.

The hydrocarbon group having 1 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) is an alkyl group, 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 a hydrocarbon group, a C1-C10 thing is preferable.

  Specific examples of the unsubstituted hydrocarbon group are, 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; such as benzyl, 2-phenylethane-1-yl, 3-phenylpropan-1-yl, 1-naphthylmethyl, 2-naphthylmethyl and the like Alkyl aromatic hydrocarbons linked by a chain.

The alkyl chain of the above hydrocarbon group is -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO _2- , -NR ^16- , -NR ^{16 -CO -, - CO-NR 16} -, - NR 16 -COO -, - OCO-NR 16 - or ^-SiR 17 ^{R 18} - may be interrupted by. The hydrogen atom in the hydrocarbon group is a halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom, cyano group, nitro group, hydroxyl group, thiol group, amino group (-NH ₂ ), carboxyl group (-COOH Or 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-mentioned substituent. In addition, interruption and substitution of the alkyl chain of the above-mentioned hydrocarbon group may be combined.

The heterocyclic group having 2 to 20 carbon atoms represented by R ^{11 to} R ¹⁴ and R ^{21 to} R ^{78 and} R ^{15 in the} partial structural formulas (1-1) to (1-10) is an alicyclic group. Heterocyclic groups and aromatic heterocyclic groups can be mentioned. Specific examples of the heterocyclic group which is unsubstituted are tetrahydrofuran group, dioxolanyl group, tetrahydropyranyl group, morpholinyl furan group, thiophene group, methylthiophene group, hexylthiophene group, benzothiophene group, pyrrole group, pyrrolidine group, Examples include imidazole, imidazolidine, pyrazole, pyrazolidine, piperidine and piperazine. Further, examples of the heterocyclic group having a substituent, the above heterocyclic ^group, a hydrocarbon group of ^{R 11 ~R 14, R 21 ~R} 78 and having 1 ^to 20 carbon atoms ^{and R 15} represents And the heterocyclic group substituted with the same one as the non-substituted hydrocarbon group described in the above.

The alkylene moiety in these heterocyclic groups and the bonding site between the heterocyclic ring and the alkyl group are -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-,- _{^{SO 2 -, - NR 16 -}} , - NR 16 -CO -, - CO-NR 16 -, - NR 16 -COO -, - OCO-NR 16 - or ^-SiR 17 ^{R 18} - may be interrupted by . However, these interrupted divalent groups are not adjacent to each other. R ^{16 to} R ¹⁸ are the same as the hydrocarbon group 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) is a substituted or unsubstituted one, and R ^{11 to} R ¹⁴ and R ^{21 to} R ⁷⁸ and the same groups as those described for R ¹⁵

When R ¹ and R ² are a ring containing a nitrogen atom formed by linking to each other, the other atoms constituting the ring include a carbon atom and an oxygen atom, and the ring is a 5- or 6-membered ring Some are preferred. Preferred specific examples of the ring formed by linking R ¹ and R ² include, as a group containing a nitrogen atom to which it is bound, a pyrrole group, a pyrrolidine group, an imidazole group, an imidazolidine group, a pyrazole group, a pyrazolidine group And a piperidine group, a piperazine group and the like are mentioned, preferably a pyrrolidine group, an imidazole group, a piperidine group and a piperazine group. A benzene ring may be condensed to these rings, and may have a substituent. As a substituent, an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, methylol group, ethylol group, propyrrole group, butyrole And hydroxyalkyl groups such as groups.

  Although the following isomers exist in the compound represented by General formula (1), it is the same in the effect of this invention, and any compound can be used similarly.

As a compound represented by General formula (1), from the point which is excellent in the curability of the photosensitive resin composition,
Compound R ¹ or R ² is a phenyl group; Compound neither a hydrogen atom of R ¹ and R ^2; compounds R ¹ and R ² are linked together to form a ring are preferred, R ¹ and R More preferred are compounds in which ² is linked to each other to form a pyrrolidine ring, an imidazole ring, a piperidine ring or a piperazine ring.

  As specific examples of the compound represented by the general formula (1), compound No. 1 shown below is exemplified. 1 to No. 18 can be mentioned. However, the compound represented by General formula (1) does not receive a restriction | limiting at all by the following compounds.

The compound represented by the general formula (1) is not particularly limited, and can be produced, for example, by the method of the following reaction formula. That is, the ketone body (2) is reacted with a Lawesson's reagent to synthesize a thioketone body (3), and the hydroxylamine is further reacted under basic conditions to synthesize an 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 the amine (5). In the following reaction formula, A ¹ , R ¹ and R ² are the same as in the above general formula (1).

  In the photosensitive resin composition of the present invention, the component (A) contains at least one compound represented by the above general formula (1). The content of the compound of the present invention in the component (A) is preferably 1 to 100% by mass, more preferably 50 to 100% by mass. The other components of the (A) 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 the present invention, the content of the component (A) is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component (B). If the content of the component (A) is less than 1 part by mass, curing failure may occur due to insufficient sensitivity, and if it exceeds 20 parts by mass, volatiles may be increased during light irradiation or heating. is there.

<(B) Curable resin>
Component (B) used in the present invention is an anionically polymerizable functional group or a resin whose base is used as a catalyst to lower the curing temperature, and is a curable resin which 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 above-mentioned anionically polymerizable functional group means a functional group which can be polymerized by a base generated from a photobase generator by active energy rays such as ultraviolet light, and, for example, epoxy group, episulfide group, cyclic monomer (σ-valerolactone, (ε-caprolactam) and the like, and as a resin whose base is used as a catalyst and the curing temperature is lowered, urethane bond formation reaction with isocyanate and alcohol, addition reaction of epoxy and hydroxyl group, addition reaction of epoxy and carboxylic acid group, epoxy and What utilized the addition reaction of a thiol group, the Michael addition reaction of a (meth) acryl group, the dehydration condensation reaction of a polyamic acid, etc. is mentioned. Examples of the component (B) include epoxy resin, oxetane resin, polyamide resin, polyurethane resin, nylon resin, polyester resin and the like. These resins may be used alone or in combination of two or more. Among them, epoxy resins are preferable in terms of rapid reaction progress and good adhesion.

  Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcine, pyrocatechol, phloroglucinol and the like; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (ortho cresol) , Ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, isopropylidene bis (ortho cresol), 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 sulfophenol, sulfobisphenol, oxybisphenol, phenol novolak, ortho cresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol 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 and aromatic such as acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Or glycidyl esters of alicyclic polybasic acids, and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidyl aniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, Epoxy compounds having a glycidyl amino group such as diglycidyl ortho toluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6 -Methyl Epoxides 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 -Epoxidized conjugated diene polymers such as butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate. Also, these epoxy resins may be those which are internally crosslinked by prepolymers of terminal isocyanates or those which are polymerized 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, and those having a glycidyl group having two or more functional groups are more preferable, from the viewpoint of excellent curability. These may be used alone or in combination of two or more.

  The oxetane resin is a compound having a four-membered cyclic ether (oxetanyl group) in the molecule. Specific examples thereof include 3-ethyl-3-hydroxymethyl oxetane, 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 novolac oxetane, 1,3-1,3 Examples include bis [(3-ethyl oxetan-3-yl) methoxy] benzene, oxetanyl silsesquioxane, oxetanyl silicate and the like. These may be used alone or in combination of two or more.

  As a polyamide resin, as an acid dianhydride, ethylene tetracarboxylic acid dianhydride, 1,2,4,5-benzenetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Anhydrides and diamines include (o-, m- or p-) phenylenediamine, (3,3'- or 4,4'-) diaminodiphenyl ether, diamino benzophenone nonone, (3,3'- or 4,4 The resin which uses'-) diamino diphenyl methane etc. as a raw material is mentioned. These may be used alone or in combination of two or more.

  As a polyurethane resin, as a diisocyanate, a polyfunctional isocyanate such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and a polyol (polyfunctional alcohol) such as polyether polyol, polyester polyol, polycarbonate polyol, etc. are used as raw materials. Resin etc. are mentioned. Moreover, as nylon resin, resin etc. which used cyclic monomers, such as (epsilon) -caprolactam and lauryl lactam, as a raw material are mentioned. Moreover, as polyester resin, resin etc. which used cyclic monomers, such as delta-valerolactone and beta-propiolactone, as a raw material are mentioned. These may be used alone or in combination of two or more.

<(C) Alkali developable resin>
The photosensitive resin composition of this invention can use (C) alkali-developable resin (Hereinafter, it is also called "(C) component") in order to pattern using an alkaline solution. The component (C) is a resin which contains at least one functional group of a phenolic hydroxyl group, a thiol group and a carboxyl group and is developable 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 compounds having two or more phenolic hydroxyl groups include phenol novolac resin, alkylphenol borac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinyl phenols, bisphenol F Well-known and commonly used phenol resins such as bisphenol S-type phenol resin, poly-p-hydroxystyrene, condensation product of naphthol and aldehyde, condensation product of dihydroxynaphthalene and aldehyde and the like can be mentioned. 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 of them, 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 has various frame | skeleton synthesize | combined using etc. and. These may be used alone or in combination of two or more.

  As the carboxyl group-containing resin, known carboxyl group-containing resins can be used. The resin composition can be made alkali developable by the presence of the carboxyl group. In addition to the carboxyl group, a compound having an ethylenically unsaturated bond in the molecule may be used, but in the present invention, as a carboxyl group-containing resin, for example, it 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 singly 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 (which may be any of an oligomer and a polymer).

(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 or isobutylene. In addition, lower alkyl refers to a C1-C5 alkyl group.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, and carboxyl group-containing dialcohol compounds such as dimethylol propionic acid and dimethylol butanoic 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 type polyol, a polyolefin type polyol, an acrylic type polyol, a bisphenol A type 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 and 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 the terminal of a urethane resin by the 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) Of difunctional epoxy resins such as diisocyanate and bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bixylenol epoxy resin, biphenol epoxy resin, etc. The carboxyl group-containing urethane resin by the polyaddition reaction of a meta) acrylate or its partial acid anhydride modified substance, a carboxyl group-containing dialcohol compound, and a diol compound.

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

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

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

(8) The polyfunctional epoxy resin exemplified as the component (B) is reacted with a saturated monocarboxylic acid, and a hydroxyl group present in the side chain is a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. Carboxyl group-containing resin added with

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

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

(11) Non-photosensitive carboxyl obtained by reacting 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 reacted with a saturated monocarboxylic acid, and the reaction product obtained is A carboxyl group-containing resin obtained by reacting a basic acid anhydride.

(13) A reaction product obtained by reacting an unsaturated group-containing monocarboxylic acid 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 A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a substance.

(14) A reaction product obtained by reacting a saturated monocarboxylic acid 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 Carboxyl group-containing resin obtained by reacting polybasic acid anhydride with

(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) 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 is reacted 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 A reaction with an acid is carried out, and a polybasic anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid or the like is reacted to the alcoholic hydroxyl group of the reaction product obtained Carboxyl group-containing resin obtained by

(18) reacting an epoxy compound having a plurality of epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, A carboxyl group obtained by reacting an alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid and the like 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, (meth) With respect to the alcoholic hydroxyl group of the reaction product obtained by reacting with unsaturated group-containing monocarboxylic acid such as acrylic acid, 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) The resin according to any one of the above (1) to (19) may further contain one epoxy group and one or more (meth) acryloyl groups in a molecule such as glycidyl (meth) acrylate or α-methylglycidyl (meth) acrylate. A carboxyl group-containing resin formed by adding a compound having a group.

  Examples of compounds having a thiol group include trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, and trimethylolpropane tris. Thioglycollate, 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 compounding amount of the component (C) is preferably 50 to 1000 parts by mass, and less than 50 parts by mass with respect to 100 parts by mass of the component (B). If it is more than 1000 parts by mass, curing failure may occur at the time of energy beam irradiation.

<(D) Additive>
In the photosensitive resin composition of the present invention, as optional components, (D) additives such as an inorganic compound, a coloring material, a latent epoxy curing agent, a chain transfer agent, a sensitizer and a solvent (hereinafter referred to as “(D) Component) can be used.

  As the inorganic compound, for example, 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 minerals, miloli blue, calcium carbonate, carbonate Magnesium, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum silicate, aluminum hydroxide, platinum, gold , Silver, copper and the like. These inorganic compounds are used, for example, as a filler, an antireflective agent, a conductive material, a stabilizer, a flame retardant, a mechanical strength improver, a special wavelength absorber, an ink-emitting agent and the like. These inorganic compounds may be used alone or in combination of two or more.

  Examples of coloring materials include pigments, dyes, and natural dyes. These colorants can be used alone or in combination of two or more.

As the pigment, for example, nitroso compound; nitro compound; azo compound; diazo compound; xanthene compound; quinoline compound; anthraquinone compound; coumarin compound; Perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalenetetracarboxylic acids; azo dyes, metal complex compounds of cyanine dyes; lake pigments; furnace method, channel method or thermal method Carbon black, or carbon black such as acetylene black, ketjen black or lamp black; Prepared or coated with an epoxy resin, the above carbon black previously dispersed in a solvent with a resin, and adsorbed with a resin of 20 to 200 mg / g, the above carbon black subjected to an acid or alkaline surface treatment, an 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 total amount of oxygen calculated from CO and CO ₂ in volatile components at 950 ° C., 9 mg or more per 100 m ^{2 of} surface area; Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon micro coil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese system, The Erocyanides, phosphate blue, bitumen, ultramarine, cerulian blue, pyridinium, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), 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.

  As the pigment, commercially available pigments can also be used. For example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 31, 38, 41, 48, 49, 88, 90, 97 , 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223 , 224, 226, 227, 228, 240, 254; pigment oranges 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 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, Dyes, such as a cyanine dye, etc. are mentioned, You may mix and use these plurality.

  Examples of the latent epoxy curing agent include dicyandiamide, modified polyamines, hydrazides, 4,4'-diaminodiphenyl sulfone, boron trifluoride amine complex salt, imidazoles, guanamines, ureas and melamine. A plurality of may be mixed and used.

  As a chain transfer agent or a 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- 3- Mercapto compounds such as mercapto propionates, Disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acids, iodoacetic acids, iodopropionic acids, 2-iodoethanol, 2-iodoethanesulfonic acid, iodos such as 3-iodopropanesulfonic acid Alkylated compounds, 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 Aliphatic polyfunctional thiol compounds such as trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropyl thioxanthone, the following compound D1 and the like And Kalens MT BD1, PE1, NR1 and the like manufactured by Showa Denko K. K.

  As the above-mentioned solvent, usually, a solvent capable of dissolving or dispersing the above-mentioned each component ((A) component, (B) component and (C) component etc.), for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl Ketones such as isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and 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 and texanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Cellosolv solvents such as alcohol; 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 acetate Ether ester solvents such as ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; hexane, heptane, octane, cyclohexane and the like Aliphatic hydrocarbon solvents; terpene hydrocarbon oils such as turpentine oil, D-limonene, pinene; mineral spirit, swasol # 310 (Cosmo Matsuyama Oil Co., Ltd.), SO 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 aromatic compounds such as chlorobenzene Hydrocarbon solvents; Carbitol solvents; Aniline; Triethylamine; Pyridine; Acetic acid; Acetonitrile; Carbon Disulfide; N, N-Dimethylformamide; N, N-Dimethylacetamide; N-Methylpyrrolidone; Dimethylsulfoxide; These solvents can be used alone or as a mixture 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 viewpoint 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, and each component is uniformly dispersed or dissolved, and a liquid to paste form in which the photosensitive resin composition of the present invention is suitable for each use. The amount of the solid content (all components other than the solvent) in the photosensitive resin composition of the present invention is preferably 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 halides and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, 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 isocyanate group, methacryloyl group or epoxy group such as KBE-9007, KBM-502, KBE-403 etc. Coupling agents are preferably used.

As the melamine compound, all or part (CH ₂ OH group) of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, and (poly) methylolurea The compound etc. which alkyletherified at least 2 can be mentioned. Here, as an alkyl group which comprises an alkyl ether, a methyl group, an ethyl group, or a butyl group is mentioned, You may mutually be same or different. Moreover, the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result.

  Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Among these, alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable from the viewpoint of solubility in a solvent and difficulty in crystal precipitation from a photosensitive resin composition.

  In the photosensitive resin composition of the present invention, the amount of the optional components other than the component (A), the component (B) and the component (C) (but excluding the inorganic compound, the coloring material and the solvent) is the purpose of use Although it selects suitably according to and it does not restrict | limit in particular, Preferably it is 50 mass parts or less in total with respect to 100 mass parts of (B) components.

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

  (1) As a process of forming the coating film of the photosensitive resin composition of this invention on a board | substrate, it is known means, such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, immersion. It can be applied on a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic and the like. In addition, once applied on a supporting substrate such as a film, it can be transferred onto another supporting substrate, and the method of application is not limited. In addition, when the photosensitive resin composition contains a solvent, it is preferable to remove a solvent using a hotplate, oven, etc. after application.

  (2) In the step of irradiating the coating film with energy rays (light) through a mask having a predetermined pattern shape, a light source of energy rays used includes an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a medium pressure mercury lamp , 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 radiation such as energy, electron beam, X-ray and radiation can be used, but preferably, ultra-high pressure mercury lamp, mercury vapor arc lamp, carbon arc lamp, xenon arc which emits light of wavelength 300 to 450 nm A lamp or the like is used.

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

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

  (4) In the step of developing the film after exposure, as an alkaline developer, a water-soluble organic solvent, a surfactant, and the like are added to an aqueous solution of an alkaline compound as required. Examples of the alkaline compound in the alkaline developer include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene and the like Examples thereof include cyclic tertiary amines, tetramethyl ammonium hydroxide, amines such as tetraethyl ammonium hydroxide, and ammonium compounds. In addition, not only an alkaline developing solution but the organic solvent can also be used for patterning of the photosensitive resin composition of this invention, and a cyclopentanone etc. are mentioned as an organic solvent used.

  (5) The step of heating the film after development is not an essential step, but it is preferable because the hardness of the cured film is further improved. Post-baking 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 an oven.

  The photosensitive resin composition of the present invention is a photoresist for electronics; electroplating resist; etching resist; dry film; solder resist; for producing color filters for various display applications, or plasma display panel, electroluminescence Display devices, and resists for forming those structures in the manufacturing process of LCDs; compositions for encapsulating electric and electronic parts; solder resists; magnetic recording materials; micromechanical parts; waveguides; Masks; Etching masks; Color test systems; Glass fiber cable coatings; Stencils for screen printing; Materials for producing three-dimensional objects by stereolithography; Microelectronic circuits; Photoresist materials for printed wiring boards; UV and visible lasers direct Photoresist materials for imaging 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 coloring material is added is suitably used as a resist constituting each pixel such as RGB in a color filter, or 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 an ink jet color filter partition having a profile angle of 50 ° or more. As the ink repellent agent, a composition containing a fluorine-based surfactant and a fluorine-based surfactant is suitably used.

  When it is used as a partition for an ink jet system color filter, the partition formed from the photosensitive resin composition of the present invention partitions the transferred body, and the droplets are applied to the recessed portion on the partitioned transfer body by the inkjet method The optical element is manufactured by the method of forming the image area. Under the present circumstances, it is preferable that the said droplet contains a coloring agent and the said image area | region is colored, and in that case, the optical element produced by said manufacturing method is from several colored area on a board | substrate And at least a partition that separates each colored area of the pixel group.

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

  The insulating film is used for the insulating resin layer in the laminate in which the insulating resin layer is provided on the peelable support base material, and the laminate can be developed with an alkaline aqueous solution, and the insulating resin layer 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 fired product patterns such as partition patterns, dielectric patterns, electrode patterns and black matrix patterns of plasma display panels.

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

  The novel compounds of the present invention have high chemical stability and excellent thermal stability, and can be used as the component (A) of the photosensitive resin composition described above, as well as chemically amplified resists, etc. It can be used.

  Hereinafter, the present invention will be described in more detail by way of examples and experimental examples, but the present invention is not limited to these examples and the like.

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

A solution of 2.4 g (12 mmol) of 4-nitrophenyl chloroformate and 3 mL of chloroform was added dropwise to a solution of 2.0 g (11 mmol) of the resulting oxime compound, 2.2 g (22 mmol) of triethylamine and 10 mL of chloroform under ice-water cooling After stirring for 1.5 hours, 1.0 g (12 mmol) of piperidine was added dropwise. After stirring for 4 hours at room temperature, water was added to conduct oil-water separation, and the oil layer was washed with water. The oil layer is dried over anhydrous magnesium sulfate and desolvated under reduced pressure to give an oil, which is purified by silica gel column chromatography (toluene / ethyl acetate = 5: 1) to obtain 1.1 g of a yellow solid having a melting point of 214 ° C. The rate is 34%). It was confirmed by ¹ H-NMR and IR spectrum that the obtained compound is the desired product. The results are shown in Tables 2 and 3.

[Examples 1-2 to 1-6] Compound No. 1 2 to 5 and no. Synthesis of Compound No. 9 Compound No. 9 was prepared in the same manner as in Example 1. 2 to 5 and no. 9 was synthesized. Physical property data and the like are shown in Tables 1 to 3.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）

¹ H-NMR (CDCl ₃ )

  In Table 2, a proton number of 0.5 H means 1 H of either isomer, and 1.5 H means 3 H 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 Remaining Rate of Compound Compound Nos. 2-1 and 2-2 and Comparative Example 2-1. The remaining rate of the compound was evaluated using 4, 5 and a comparison compound. First, the compound No. Each was dissolved in a solvent of acetic acid / water = 9: 1 such that the content of 4, 5 and the comparative compound was 0.1% by mass. The resulting solution was heated for 3 hours while being stirred at 80 ° C. The compound residual rate after 3 hours when the post-dissolution (0 hour) was taken as the initial value was calculated. In addition, in calculation of the compound residual rate, high performance liquid chromatography (HPLC) was used for the analysis. The obtained results are shown in Table 4 below.

[Examples 3-1 to 3-6] Preparation Example of Photosensitive Resin Composition and Evaluation Example 1
5 parts by mass of the compounds listed in Table 5 below as component (A), 52 parts by mass of EP-4901 (bisphenol F type glycidyl ether manufactured by ADEKA) as component (B), and (D) as an additive component 43 parts by mass of Kalens MT BD1 (manufactured by Showa Denko K. K., epoxy curing agent) was mixed, and the mixture was kneaded with a three-roll mill to obtain photosensitive resin compositions. The resulting photosensitive resin composition was heated at 60 ° C. for 60 minutes without irradiation with UV light from an ultrahigh pressure mercury lamp and after irradiation with 200 mJ / cm ² UV light, and the curing ratio was measured. The curing rate is (peak intensity at 3,450 cm ⁻¹ ) / (peak intensity at 1,510 cm ⁻¹ in FT-IR when cured at 120 ° C. for 60 minutes after UV light irradiation at 5,000 mJ / cm ² It calculated | required as a relative value by making the value of) into 100% of a hardening rate. The results are shown in Table 5 below.

[Examples 4-1 to 4-12] Preparation Example of Photosensitive Resin Composition and Evaluation Example 2
After blending according to the composition ratio described in Tables 6 and 7 below, the photosensitive resin composition of the present invention was produced by kneading with a three-roll mill. The obtained photosensitive resin composition was applied onto a glass substrate (adjusted to have a film thickness of 6 μm after prebaking), and dried on a 90 ° C. hot plate for 2 minutes. After irradiating 250 mJ / cm ^{2 with a} high pressure mercury lamp (manufactured by HOYA CANDEO OPTRONICS CORPORATION, irradiation illuminance 20 mW / cm ² ), heating was performed 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.

<Curable>
The film thickness after development when the film thickness before development is 100 is shown. The closer to 100, the higher the curability and the better the development resistance. The developing solution used for evaluation used the aqueous alkali solution (henceforth a TMAH developing solution) adjusted so that the tetramethyl ammonium hydroxide (TMAH) containing 5 mass% of ethanolamines might be 3 mass%.

<Developability>
When development was possible with cyclopentanone (organic solvent), when development was possible with TMAH developer ◎, development was possible with cyclopentanone, and when development was not possible with TMAH developer ○ In the case where even cyclopentanone could not be developed, it was evaluated 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. 5 Compound 5 <(B) Component>
EPPN-201: Phenolic 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 <(C) component>
TRR-5010G: cresol novolak type phenol resin, hydroxyl equivalent 120 g / eq. Mw = 8,000, manufactured by Asahi Organic Materials Co., Ltd. GDP-6095LR: Dicyclopentadiene modified phenolic resin, hydroxyl equivalent 168-171 g / eq. Mw = 443, manufactured by Gunei Chemical Industry Co., Ltd. Copolymer 1: Styrene-methyl methacrylate copolymer, styrene / methyl methacrylate = 80/20, Mw = 8,000, acid value = 14 mg HOH / g
<Non-alkali developable resin>
Non-alkali developable phenol novolac type phenol resin, hydroxyl 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 (9)

The following general formula (1 '),

(In the general formula (1 ′), ring A ¹ is any of the following partial structural formulas (1-1) to (1-10), and R ¹ and R ² are each independently a hydrogen atom or no atom A substituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a ring containing a nitrogen atom formed by linking R ¹ and R ² to each other, a 5-membered member represented by ring A ¹ When the atoms constituting the 8-membered ring do not contain a nitrogen atom, R ¹ and R ² are rings formed by linking each other, and the ring is optionally selected from a nitrogen atom, an oxygen atom and a carbon atom A novel compound characterized by being formed and represented by a benzene ring which may be fused to the ring.

(Wherein, * represents a site linked to a nitrogen atom through a double bond in the general formula (1 ′), and X each independently represents —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 R ¹⁵ represents a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or unsubstituted or substituted It represents a C2-C20 heterocyclic group having a substituent. The novel compound according to claim 1, wherein R ¹ and R ² are a ring containing a nitrogen atom formed by linking to each other. The novel compound according to claim 1 or 2, wherein ring A ¹ is represented by the following partial structural formula (1-2).

(Wherein, * represents a site linked to a nitrogen atom through a double bond in the general formula (1 ′), X represents —NR ¹³ —, and R ¹³ independently represents a hydrogen atom. And a nitro group or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ^{25 to} R ³⁰ each independently represent a hydrogen atom or a nitro group.)   The novel compound according to claim 3, wherein the unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms is an alkyl group having 1 to 20 carbon atoms. The novel compound according to claim 1 or 2, wherein ring A ¹ is represented by the following partial structural formula (1-4).

(Wherein, * represents a site linked to a nitrogen atom by a double bond in the general formula (1 ′), X represents —CO—, —CS—, —NR ¹³ —, R ¹³ Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ^{35 to} R ^{40 each} represent a hydrogen atom.)   The novel compound according to claim 5, wherein the unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms is an alkyl group having 1 to 20 carbon atoms. The novel compound according to claim 1 or 2, wherein ring A ¹ is represented by the following partial structural formula (1-10).

(Wherein, * represents a site linked to a nitrogen atom by a double bond in the general formula (1 ′), X represents —S—, and R ^{71 to} R ⁷⁸ each independently represent Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.)   The novel compound according to claim 7, wherein the unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms is an alkyl group having 1 to 20 carbon atoms. The novel compound according to any one of claims 1 to 8, which is for a photobase generator.