JP4726868B2 - Alkali-developable photosensitive resin composition - Google Patents

Description

  The present invention relates to an alkali-developable photosensitive resin composition containing a specific compound imparted with an ethylenically unsaturated bond, and an alkali development obtained by further adding a photopolymerization initiator to the alkali-developable photosensitive resin composition. The present invention relates to a photosensitive photosensitive resin composition.

  Usually, the alkali-developable photosensitive resin composition contains an alkali-developable resin composition containing a compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since this alkali-developable photosensitive resin composition can be polymerized and cured by irradiating with ultraviolet rays or electron beams, various photo-curable inks, photosensitive printing plates, printed wiring plates, liquid crystal display color filters, etc. Used in photoresists and the like. In recent years, with the progress of miniaturization and high functionality of electronic devices, an alkali-developable photosensitive resin composition capable of forming a fine pattern with high accuracy is desired.

  In addition, the photopolymerization initiator used in the alkali-developable photosensitive resin composition is expensive, and unreacted components and decomposition products of the photopolymerization initiator remain in the coating film and cause contamination. There has been a demand for an alkali-developable photosensitive resin composition that does not use an initiator or reduces the amount used, is excellent in sensitivity and adhesion, and can form a fine pattern with high accuracy.

  On the other hand, in the following Patent Documents 1 to 4, a photocurable composition in which a reaction product obtained by adding a β-diketone compound to a compound containing an acryloyl group is cured without using a photopolymerization initiator. Although it is described that it can be used as an alkali-developable photosensitive resin composition, no example is described.

Japanese Patent No. 3649331 JP 2003-268025 A JP 2006-241461 A US Pat. No. 5,459,178

  As described above, the problems to be solved are excellent in sensitivity and adhesion, and can obtain an appropriate pattern shape and fine pattern, even though a photopolymerization initiator is not used or a small amount is used. This means that there has never been an alkali-developable photosensitive resin composition.

  Accordingly, an object of the present invention is to provide an alkali-developable photosensitive resin composition that is excellent in sensitivity and adhesion, and can form a fine pattern with high precision, even though a photopolymerization initiator is not used or is used in a small amount. It is to provide.

  In the present invention, a compound having a β-diketone moiety or a compound having a β-ketoester group or a compound having a β-ketoester group is added to the (meth) acryloyl group of the compound (A) having two or more (meth) acryloyl groups and a hydroxyl group. A photopolymerizable unsaturated compound (J) having a structure obtained by an esterification reaction between the hydroxyl group of the reaction product obtained by the reaction and the polybasic acid anhydride (C). A photosensitive resin composition is provided.

  Further, the present invention provides a structure in which the compound (A) having two or more (meth) acryloyl groups and a hydroxyl group is a reaction product obtained by adding an unsaturated monobasic acid (E) to an epoxy compound (D). The alkali-developable photosensitive resin composition having the above is provided.

（式中、Ｃｙは炭素原子数３〜１０のシクロアルキル基を示し、Ｘは水素原子、フェニル基又は炭素原子数３〜１０のシクロアルキル基を示し、該フェニル基及びシクロアルキル基は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基又はハロゲン原子により置換されても良く、Ｙ及びＺはそれぞれ独立して、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を示し、該アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｎは０〜１０の数を示し、ｐ及びｒはそれぞれ独立して、０〜４の数を表す。） Moreover, this invention provides the said alkali developable photosensitive resin composition whose said epoxy compound (D) is a structure represented by the following general formula (I).

(In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a hydrogen atom, a phenyl group or a cycloalkyl group having 3 to 10 carbon atoms, and the phenyl group and the cycloalkyl group are carbon atoms. The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms or the halogen atom may be substituted, and Y and Z are each independently an alkyl group having 1 to 10 carbon atoms and 1 carbon atom. Represents an alkoxy group having 10 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and n represents a number from 0 to 10 , P and r each independently represents a number of 0 to 4.)

  In addition, the present invention provides the alkali-developable photosensitive resin composition in which, in the general formula (I), Cy is a cyclohexyl group, X is a phenyl group, and p and r are 0. .

  Moreover, this invention provides the said alkali-developable photosensitive resin composition which contains a photoinitiator (F) further.

  The present invention also provides a colored alkali-developable photosensitive resin composition obtained by further adding a colorant (G) to the alkali-developable photosensitive resin composition.

  The alkali-developable photosensitive resin composition of the present invention provides sufficient sensitivity, resolution and adhesion without using a photopolymerization initiator or using a small amount.

  Hereinafter, the alkali-developable photosensitive resin composition of the present invention will be described in detail based on preferred embodiments.

  The alkali-developable photosensitive resin composition of the present invention is a compound or β-ketoester having a β-diketone moiety in the (meth) acryloyl group of the compound (A) having two or more (meth) acryloyl groups and hydroxyl groups. Contains a photopolymerizable unsaturated compound (J) having a structure obtained by esterification reaction of a hydroxyl group of a reaction product obtained by adding a compound (B) having a group and a polybasic acid anhydride (C) To do.

  The compound (A) is sandwiched between a hydrogen atom of a methylene group sandwiched between diketones in the β-diketone portion of the compound (B) or a keto ester in a β-ketoester group with respect to one (meth) acryloyl group. The proportion of hydrogen atoms in the methylene group is preferably 0.1 to 1.0, more preferably 0.3 to 1.0, and the polybasic group is used for one hydroxyl group of the reaction product. The ratio of the acid anhydride structure of the acid anhydride (C) is preferably 0.1 to 1.0, more preferably 0.3 to 0.9.

  In the present invention, the compound (A) having two or more (meth) acryloyl groups and a hydroxyl group includes t-1 hydroxyl groups of a polyol compound having 3 to t hydroxyl groups, and an unsaturated monobasic acid. (E) is a derivative having a structure that is an esterification reaction product, a derivative having 3 to t hydroxyl groups, wherein a hydroxy acid or alkylene oxide is added to a polyol represented by the following general formula (II) Unsaturated monobasic acid (E) was added to the epoxy compound (D) having a structure that is an esterification reaction product of t-1 hydroxyl groups and unsaturated monobasic acid (E). The thing etc. which are the structures which are reaction products are mentioned.

Z ₁ (OH) _a (—O—CO—R—OH) _b [— (OR) _n —OH] _c (II)
(In the formula, Z ₁ is a polyol residue, a, b and c are a total number of 3 or more, and R represents an alkanediyl group such as methylene, ethylene, propylene, trimethylene, butylene, tetramethylene, etc.) , N represents 1 to 15.)

  The ratio of the carboxyl group of the unsaturated monobasic acid (E) to one epoxy group of the epoxy compound (D) is preferably 0.1 to 1.0, more preferably 0.5 to 1. .0.

  Specific examples of the compound (A) include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, trimethylolethane diacrylate, trimethylolpropane diacrylate, tetramethylolpropane triacrylate, and 2-hydroxy-3-acryloyl. Roxypropyl acrylate and the following compound No. 1A etc. are mentioned.

  The number of (meth) acryloyl groups in the compound (A) is preferably 2 to 10, more preferably 2 to 6, and the number of hydroxyl groups is preferably 1 to 8, and more preferably 1 to 4. This is because an alkali-developable photosensitive resin composition having excellent developability and adhesion can be obtained.

  As an example of the said epoxy compound (D), what is the structure represented by the polyfunctional epoxy compound mentioned below and the said general formula (I), etc. are mentioned.

Examples of the polyfunctional epoxy compound include bisphenol type epoxy compounds and glycidyl ethers, and examples of the bisphenol type epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, and bis (hydroxyphenyl) fluorene type epoxies. In addition to alkylidene bisphenol polyglycidyl ether type epoxy resins such as compounds, bisphenol type epoxy compounds such as hydrogenated bisphenol type epoxy compounds can be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,8-octanediol diglycidyl ether. 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol di Glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1 Tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, include 1,1,1,1- tetra (glycidyloxymethyl) methane.

  Other examples of the polyfunctional epoxy compound include phenol novolac epoxy compounds, (o-, m-, p-) phenylphenol novolac epoxy compounds, (o-, m-, p-) cresol novolac epoxy compounds, o-, m-, p-) novolak type epoxy compounds such as halogenated phenol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds, bisphenol F novolak type epoxy compounds, naphthol novolak type epoxy compounds; A novolak-type epoxy compound formed by condensation polymerization of the epoxy compound and an aromatic hydrocarbon; an addition-reaction type epoxy compound of the epoxy compound and dicyclopentadiene; 3,4-epoxy-6-methylcyclohexylme 3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2,2-bis (3,4-epoxycyclohexyl) Alicyclic epoxy compounds such as propane and 1-epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate and glycidyl dimer; tetraglycidyl diaminodiphenylmethane, tri Glycidylamines such as glycidyl-p-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as lopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds; addition polymers of (o-, m-, p-) hydroxystyrene or (o-, m An epoxy compound obtained by glycidyl etherification of a hydroxyl group of a copolymer of-, p-) hydroxystyrene and ethylene and / or propylene can be used.

  Among these epoxy compounds (D), those represented by the above general formula (I) are preferable because of their good properties as epoxy resins.

  In the general formula (I), examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Cy include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Can be mentioned.

In the general formula (I), examples of the cycloalkyl group having 3 to 10 carbon atoms represented by X include those exemplified as the cycloalkyl group having 3 to 10 carbon atoms represented by Cy. The phenyl group represented by X or the cycloalkyl group having 3 to 10 carbon atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Examples of the group include those exemplified later as those represented by Y and Z.
Examples of the alkyl group having 1 to 10 carbon atoms represented by Y and Z include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, Examples include heptyl, octyl, isooctyl, t-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl and the like. Examples of the alkoxy group having 1 to 10 carbon atoms represented by Y and Z include, for example, methoxy, ethoxy, propyloxy, butyloxy, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxy Examples include ethyl and methoxypropyl. Examples of the alkenyl group having 2 to 10 carbon atoms represented by Y and Z include vinyl, allyl, butenyl, propenyl, etc. Examples of the halogen atom represented by Y and Z include fluorine, chlorine, bromine and iodine. Is mentioned.
In addition, the phenyl group represented by X and the cycloalkyl group having 3 to 10 carbon atoms may be substituted, and the alkyl group, alkoxy group and alkenyl represented by Y and Z. The group may be substituted with a halogen atom, and examples of the halogen atom include fluorine, chlorine, bromine and iodine. For example, as a C1-C10 alkyl group substituted by the fluorine atom, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl etc. are mentioned, for example.

  As preferable epoxy compound (D) represented by the above general formula (I) in the present invention, for example, the following compound No. 1-No. 9 etc. are mentioned. In the formula, Me represents a methyl group.

（上記化合物Ｎｏ．２において、Ｍｅ−は位置を特定していない事を表す。）

(In the above compound No. 2, Me- represents that the position is not specified.)

  Among the compounds having the structure represented by the general formula (I) in the epoxy compound (D), it is preferable that Cy is a cyclohexyl group, X is a phenyl group, and p and r are 0. This is because the raw materials are easily available and the productivity is good.

  In the present invention, the method for producing the epoxy compound (D) represented by the general formula (I) is not particularly limited. For example, as shown in the following [Chemical Formula 12], a substituted phenylcycloalkyl ketone ( A bisphenol compound (2) is obtained by reacting 1) with a phenol derivative in the presence of an acid catalyst, and is easily produced by reacting this with epichlorohydrin in the presence of an alkali or Lewis acid or a phase transfer catalyst. be able to.

  The said bisphenol compound (2) can be manufactured by conventionally well-known conditions, for example, is obtained by making it react at the temperature of 20-200 degreeC for 1 to 40 hours in presence of an acidic catalyst.

  Examples of the acidic catalyst include methanesulfonic acid, benzenesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid, hydroxymethylsulfonic acid, 2-hydroxyethylsulfonic acid, hydroxypropylsulfonic acid, trifluoromethanesulfonic acid, Sulfonic acids such as sulfosalicylic acid and sulfophthalic acid; sulfuric acid, sulfuric anhydride, fuming sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, hydrochloric acid, hydrogen chloride gas, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, silicotungstic acid, phosphorus Examples include heteropolyacids such as tungstic acid, strongly acidic ion exchange resins, activated clay, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. The acidic catalyst is preferably used in an amount of 0.1 to 70 parts by mass, more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the substituted phenylcycloalkylketone (1).

  Further, a mercaptan catalyst can be used to promote the reaction. Examples of the mercaptan catalyst include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 1,6-hexanedithiol, and the like. Alkyl mercaptans; aromatic mercaptans such as thiophenol and thiocresol; mercapto organic acids such as mercaptoacetic acid (thioglycolic acid), 3-mercaptopropionic acid, mercaptoundecanoic acid and thiobenzoic acid; 2-mercaptobenzothiazole, etc. And heterocyclic mercaptans.

  Moreover, a conventionally well-known solvent can be used for the said reaction, For example, terpene, such as aromatic hydrocarbon type solvents, such as toluene, xylene, cumene; terpine oil, D-limonene, pinene, etc. Hydrocarbon oils; mineral spirits, paraffinic solvents such as Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); alcoholic solvents such as methanol and ethanol; esters such as ethyl acetate Solvents: Halogen solvents such as dichloroethane, carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, chlorobenzene; cyclic ether solvents such as tetrahydrofuran and dioxane; ethers, cellosolve solvents, ketone solvents, aniline, triethylamine, pyridine, dioxane , Acetic acid, acetonitrile , Carbon disulfide, and the like.

The epoxy compound (D) represented by the general formula (I) can be produced from the bisphenol compound (2) and epichlorohydrin under conventionally known conditions.
For example, the reaction is carried out in the range of 20 to 100 ° C., particularly 30 to 80 ° C. in the presence of an alkali or Lewis acid or a phase transfer catalyst. If it is less than 20 ° C., the reaction is delayed and a long reaction time is required.

  Examples of the alkali used in the above reaction include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, and examples of the Lewis acid include acidic catalysts such as those exemplified above, tin tetrachloride, trifluoride. Examples thereof include boron, titanium tetrachloride, activated clay, aluminum chloride, magnesium chloride, potassium permanganate, and potassium chromate. Examples of the phase transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, and methyltrioctylammonium. Chloride, methyltridecylammonium chloride, benzyltriethylammonium chloride, N, N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N- Benzyl -Methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N- Methylmorpholinium bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N-methyl-N-ethylpiperidi Examples thereof include nium acetate and N-methyl-N-ethylpiperidinium iodide.

  The amount of epichlorohydrin used in this reaction is 1 mole or more, particularly 2 to 10 moles per 1 hydroxyl group of the bisphenol compound (2), and the alkali is 0.1 to 2 mol per hydroxyl group. 0 mol, especially 0.3 to 1.5 mol is used, and the Lewis acid or phase transfer catalyst is 0.01 to 10 mol%, particularly 0.2 to 5 mol, based on one hydroxyl group of the bisphenol compound (2). %used.

  In this reaction, a solvent as exemplified in the column of production of bisphenol compound (2) can be used. Excess epichlorohydrin can also be used as a solvent.

  The unsaturated monobasic acid (E) used in the preparation of the alkali-developable photosensitive resin composition of the present invention is used to improve the sensitivity of the alkali-developable photosensitive resin composition, for example, acrylic acid , Methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate, dicyclopentadiene malate or one carboxyl group and 2 And polyfunctional (meth) acrylates having at least one (meth) acryloyl group.

  The polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups has, for example, one hydroxyl group and two or more (meth) acryloyl groups in one molecule. It can be obtained by reacting a polyfunctional (meth) acrylate with a dibasic acid anhydride or carboxylic acid.

  Examples of the polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups include the following compound Nos. 10-No. 12 can be mentioned.

  As the compound having a β-diketone moiety or the compound having a β-ketoester group (B) used for obtaining the alkali-developable photosensitive resin composition of the present invention, 2,4-pentanedione, 2,4 -Hexanedione, 2,4-heptanedione, 1-methoxy-2,4-pentanedione, 1-phenyl-1,3-butanedione, 1,3-diphenyl-1,3-propanedione, methyl acetoacetate, aceto Ethyl acetate, isopropyl acetoacetate, butyl acetoacetate, tert-butyl acetoacetate, 2-methoxyethyl acetoacetate, 2-ethylhexyl acetoacetate, lauryl acetoacetate, allyl acetoacetate, ethyl propionyl acetate, butyl propionyl acetate, butyryl Methyl acetate, methyl benzoyl acetate, ethyl benzoyl acetate, butyric butyl acetate , Methyl 4,6-dioxoheptanoate, methyl 5,7-dioxooctanoate, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, benzyl acetoacetate, 1,4-butanediol Diacetoacetate, 1,6-hexanediol diacetoacetate, neopentyl glycol diacetoacetate, 2-ethyl-2-butyl-1,3-propanediol diacetoacetate, cyclohexanedimethanol diacetoacetate, ethoxylated bisphenol A diacetoacetate, trimethylolpropane triacetoacetate, glycerol triacetoacetate, pentaerythritol triacetoacetate, pentaerythritol tetraacetoacetate, ditrimethylolpropane tetraacetate Acetate, group-containing oligomer acetoacetic esters, acetoacetic ester group-containing oligomers or polymers obtained by transesterification reaction and polymerization of methacrylic acid-2-acetoacetoxyethyl of ethyl acetoacetate and a hydroxyl group-containing oligomer or polymer.

  Examples of the polybasic acid anhydride (C) used for obtaining the alkali-developable photosensitive resin composition of the present invention include succinic anhydride, maleic anhydride, trimellitic anhydride, phthalic anhydride, and methyltetrahydrophthalic anhydride. Monoanhydrides such as acid, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl hymic anhydride 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic anhydride, 3,3′-4,4′-benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimellitate) 2,2′-3,3′-benzophenonetetracarboxylic anhydride, 3,3 ′, 4,4′- Phenyltetrasulfonic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl- 3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, meso-butane-1,2 , 3,4-tetracarboxylic acid anhydrides and other dianhydrides, glycerol tris (anhydro trimellitate) and other dianhydrides, and dianhydrides and monoanhydrides may be combined. Monoanhydride is particularly preferable.

Reaction obtained by adding a compound having a β-diketone moiety or a compound having a β-ketoester group to a compound (A) having two or more (meth) acryloyl groups and a hydroxyl group in the present invention. In the production of the product, the compound (A) having two or more (meth) acryloyl groups and a hydroxyl group is essential, but the compound (A ′) having a (meth) acryloyl group and having no hydroxyl group is added to the present invention. In the range which does not impair the effect (500 parts by mass or less with respect to 100 parts by mass of the compound (A)), it can also be produced by mixing. The content of the photopolymerizable unsaturated compound (J) having a structure obtained by esterifying the polybasic acid anhydride (C) to the reaction product thus obtained is determined by the alkali development of the present invention. In the photosensitive photosensitive resin composition, it is preferably 1 to 70% by mass, more preferably 20 to 60% by mass, and the acid value of the solid content is preferably 20 to 100 mg · KOH / g, more preferably 50 to 100 mg · KOH. / G.
The compound (A ′) having a (meth) acryloyl group and not having a hydroxyl group includes pentaerythritol tetraacrylate, trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, ditrimethylol. Examples include propane tetraacrylate, isocyanuric acid EO-modified triacrylate, bisphenol A EO-modified diacrylate, bisphenol F EO-modified diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, and trimethylolpropane PO-modified triacrylate.

The alkali-developable photosensitive resin composition of the present invention may contain a solvent in addition to the photopolymerizable unsaturated compound (J), for example, the photopolymerizable unsaturated compound (J). When the amount is within the above preferred range, a solvent can be used for the remainder other than the photopolymerizable unsaturated compound (J). Specific examples of the solvent include those exemplified as the solvent described later. Moreover, without removing the solvent used when synthesizing the photopolymerizable unsaturated compound (J) from the components (A) to (E), it is contained in the alkali-developable photosensitive resin composition of the present invention as it is. Also good.
Moreover, (A)-(E) each component can be used by 1 type or in mixture of 2 or more types.

  The alkali-developable photosensitive resin composition of the present invention can be used as an alkali-developable photosensitive resin composition without adding a photopolymerization initiator (F), but in order to obtain a more sensitive resin composition. Further, it may be mixed with a photopolymerization initiator (F) and a solvent to form an alkali-developable photosensitive resin composition.

  In the alkali-developable photosensitive resin composition of the present invention, when the photopolymerization initiator (F) is used, the content of the photopolymerizable unsaturated compound (J) is from the alkali-developable photosensitive resin composition to the solvent. It is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, based on the total mass of all solids excluding.

  As the photopolymerization initiator (F), conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl- 1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-methylmercaptobenzoyl) propane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl Anthraquinone, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropylbenzoyl) propane, 4-butylbenzene Nzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6- Bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, the following compound No. 13, no. 14 etc. are mentioned. Among these, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one is preferable.

（式中、Ｘ¹はハロゲン原子又はアルキル基を表し、Ｒ¹¹はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ¹²はＲ、ＯＲ、ＣＯＲ、ＳＲ又はＮＲＲ’を表し、Ｒ¹³はＲ、ＯＲ、ＣＯＲ、ＳＲ又はＮＲＲ’を表し、Ｒ及びＲ’は、アルキル基、アリール基、アラルキル基又は複素環基を表し、これらはハロゲン原子及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合又はエステル結合により中断されていてもよく、また、Ｒ及びＲ’は一緒になって環を形成していてもよく、ｇは０〜５である。）

Wherein X ¹ represents a halogen atom or an alkyl group, R ¹¹ represents R, OR, COR, SR, CONRR ′ or CN, R ¹² represents R, OR, COR, SR or NRR ′, R ¹³ represents R, OR, COR, SR, or NRR ′, and R and R ′ represent an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, which are substituted with a halogen atom and / or a heterocyclic group. Among them, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R and R ′ together form a ring. It may be formed and g is 0-5.)

（式中、Ｘ¹、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ及びＲ’は上記化合物Ｎｏ．と同様であり、Ｘ¹’はハロゲン原子又はアルキル基を表し、Ｙ¹は酸素原子又は硫黄原子を表し、ｅ及びｆはそれぞれ０〜４の数を表し、Ｒ¹¹’はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ¹²’はＲ、ＯＲ、ＣＯＲ、ＳＲ又はＮＲＲ’を表し、Ｒ¹³’はそれぞれＲ、ＯＲ、ＣＯＲ、ＳＲ又はＮＲＲ’を表し、Ｒ¹⁴はジオール残基又はジチオール残基を表す。）

(In the formula, X ¹ , R ¹¹ , R ¹² , R ¹³ , R and R ′ are the same as in the above compound No., X ¹ ′ represents a halogen atom or an alkyl group, and Y ¹ represents an oxygen atom or a sulfur atom. E and f each represent a number from 0 to 4, R ¹¹ ′ represents R, OR, COR, SR, CONRR ′ or CN, R ¹² ′ represents R, OR, COR, SR or NRR ′. R ¹³ ′ represents R, OR, COR, SR or NRR ′, and R ¹⁴ represents a diol residue or a dithiol residue.)

  In the alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerization initiator (F) is preferably a proportion of the total mass of the total solid content excluding the solvent from the alkali-developable photosensitive resin composition. It is 0.01-20 mass%, More preferably, it is 0.05-20 mass%. Moreover, the said photoinitiator (F) can be used by 1 type or in mixture of 2 or more types.

The solvent contained in the alkali-developable photosensitive resin composition of the present invention is not particularly limited as long as it is a solvent that can dissolve or disperse the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone Ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone and cyclohexanone; 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, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate Cellsolve solvents of: alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; BTX solvents such as benzene, toluene, xylene; hexane, heptane, octane, cyclohexane, etc. Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.), etc. Paraffinic solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid , Acetonitrile, disulfur Carbon, N, N- dimethylformamide, N- methylpyrrolidone, and among these, ketones or cellosolve solvent. These solvents can be used alone or in combination of two or more.
In the alkali-developable photosensitive resin composition of the present invention, the content of the solvent is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total solid content in the alkali-developable photosensitive resin composition. It is good to adjust it to be%.

  The colored alkali-developable photosensitive resin composition of the present invention is obtained by adding the coloring material (G) to the alkali-developable photosensitive resin composition.

As the pigment used as the coloring material in the colored alkali-developable photosensitive resin composition of the present invention, any of the known pigments used in the production of conventional color filters can be used. Specific examples of organic pigments are shown by color index (CI) numbers below. In the list below, “x” represents C.I. I. It is an integer that can be arbitrarily selected from the numbers.
・ Pigment Blue:
<C. I> 1, 1: 2, 1: x, 9: x, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 24, 24: x, 56, 60, 61, 62
・ Pigment Green:
<C. I> 1,1: x, 2,2: x, 4,7,10,36
・ Pigment Orange
<C. I> 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 59, 60, 61, 62, 64
・ Pigment Red
<C. I> 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 3, 81: x, 83, 88, 90, 112, 119, 122, 123, 144, 146, 149, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 224, 226
・ Pigment Violet:
<C. I> 1, 1: x, 3, 3: 3, 3: x, 5: 1, 19, 23, 27, 32, 42
・ Pigment Yellow
<C. I> 1, 3, 12, 13, 14, 16, 17, 24, 55, 60, 65, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,156,175

  Further, as black pigments, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # manufactured by Mitsubishi Chemical Corporation 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, diamond black LI, diamond black LH, diamond black N339, diamond Rack SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LR, Can Curve Inc. Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Asahi Carbon Co., Ltd. Carbon Black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBl ack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, Pr, etc.

  Other pigments include miloli blue, iron oxide, titanium oxide, calcium carbonate, magnesium carbonate, silica, alumina, cobalt, manganese, talc, chromate, ferrocyanide, various metal sulfates, sulfides, selenides, Inorganic pigments such as phosphate ultramarine blue, bitumen, cobalt blue, cerulean blue, pyridiane, emerald green, and cobalt green can also be used. These pigments can be used alone or in combination of two or more.

  The dyes that can be used as the colorant (G) include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes. Examples thereof include dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like. These may be used alone or in combination of two or more.

  In the colored alkali-developable photosensitive resin composition of the present invention, the content of the colorant (G) is preferably a ratio of the total solid content excluding the solvent from the colored alkali-developable photosensitive resin composition. It is 0.5 to 70%, more preferably 5 to 60% by mass.

  In the alkali-developable photosensitive resin composition and colored alkali-developable photosensitive resin composition of the present invention, a monomer having an unsaturated bond, a chain transfer agent, a surfactant and the like can be used in combination.

Examples of the monomer having an unsaturated bond include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic Methoxyethyl acid, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Acid-t-butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Examples include tall tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate, and the like.
In the alkali-developable photosensitive resin composition of the present invention, the content of the monomer having an unsaturated bond is preferably 0 in terms of the total mass of the total solid content excluding the solvent from the alkali-developable photosensitive resin composition. 0.01 to 50% by mass, more preferably 10 to 40% by mass. These may be used alone or in combination of two or more.

  Examples of the chain transfer agent include 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, mercaptov Enol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Mercapto compounds such as pionate), disulfide compounds obtained by oxidizing the mercapto compound, iodinated alkyls such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Compounds. These may be used alone or in combination of two or more.

  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, and 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 can be used alone or in combination of two or more.

  The properties of the cured product can be improved by further using a thermoplastic organic polymer in the alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition of the present invention. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester. These may be used alone or in combination of two or more.

  In addition, for the alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition, if necessary, a thermal polymerization inhibitor such as anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; Conventional additives such as adhesion promoters, fillers, antifoaming agents, dispersants, leveling agents, silane coupling agents, flame retardants, and the like can be added. These may be used alone or in combination of two or more.

  The alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition of the present invention are prepared by known means such as spin coater, bar coater, roll coater, curtain coater, various screen printing, ink jet printing, and immersion. It is applied on a supporting substrate such as metal, paper, plastic, and glass. 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.

  The (colored) alkali-developable photosensitive resin composition of the present invention is mainly used as a (colored) alkali-developable photosensitive resin composition, mixed with the solvent, the photopolymerization initiator, and a coloring material. The (colored) alkali-developable photosensitive resin composition is not particularly limited in its use, and is a photocurable paint, a photocurable adhesive, a printing plate, a printed wiring board photoresist, a plasma display, an electroluminescence panel, It can be used for various applications such as the formation of a pixel portion of a color filter used for a video camera or a liquid crystal display, or a liquid crystal split orientation control projection.

  In addition, as an active light source used for curing the alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition of the present invention, a light source that emits light having a wavelength of 300 to 450 nm is used. For example, ultrahigh pressure mercury, mercury vapor arc, carbon arc, xenon arc, or the like can be used.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, this invention is not limited to these Examples etc. In the following examples and the like, “%” means mass%.
In Examples 1-16, the alkali developable resin composition containing a photopolymerizable unsaturated compound (J) was manufactured. Moreover, in Examples 17-32, the alkali-developable photosensitive resin composition of this invention is mixed with the alkali-developable resin composition produced in Examples 1-16 by mixing a monomer having an unsaturated bond and a solvent. Prepared. In Examples 33 to 48, the alkali-developable resin composition produced in Examples 1 to 16 was mixed with a photopolymerization initiator (F), a monomer having an unsaturated bond, and a solvent to obtain the alkali of the present invention. A developable photosensitive resin composition was prepared. In Examples 49 to 64, the colored alkali-developable photosensitive resin composition of the present invention was prepared by mixing the photopolymerization initiator (F), the colorant (G), the monomer having an unsaturated bond, and a solvent. did.

[Example 1] Alkali developable resin composition No. 1 <Step 1> Preparation of bis (4-hydroxyphenyl) -4-biphenylyl (cyclohexyl) methane 70.5 g of biphenylcyclohexyl ketone, 200.7 g of phenol and 10.15 g of thioacetic acid were charged, and trifluoromethanesulfonic acid 40. 0 g was added dropwise at 18 ° C. over 20 minutes. After reacting at 17 to 19 ° C. for 18 hours, 500 g of water was added to stop the reaction, 500 g of toluene was added, and the organic layer was washed with water until the pH became 3 to 4, and the organic layer was separated. Toluene, water and excess phenol were distilled off. Toluene was added to the residue, and the precipitated solid was filtered off and dispersed and washed with toluene to obtain 59.2 g of light yellow crystals (yield 51%). The melting point of the pale yellow crystals was 239.5 ° C., and it was confirmed that the pale yellow crystals were the target product.

<Step 2> Production of bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane Bis (4-hydroxyphenyl) -4-biphenylyl (cyclohexyl) methane 57 obtained in Step 1 0.5 g and epichlorohydrin 195.8 g were added, 0.602 g of benzyltriethylammonium chloride was added, and the mixture was stirred at 64 ° C. for 18 hours. Subsequently, the temperature was lowered to 54 ° C., 43.0 g of a 24 wt% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred for 30 minutes. Epichlorohydrin and water were distilled off, 216 g of methyl isobutyl ketone was added and washed with water, and 2.2 g of 24 wt% sodium hydroxide was added dropwise. After stirring at 80 ° C. for 2 hours, the mixture was cooled to room temperature, neutralized with a 3 wt% aqueous sodium monophosphate solution, and washed with water. The solvent was distilled off to obtain 57 g (yield 79%) of a yellow solid. (Melting point 64.2 ° C., epoxy equivalent 282, n = 0.04). The yellow crystals were confirmed to be the target product.

<Step 3> Alkali-developable resin composition No. Production of 1 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane (hereinafter also referred to as compound d-1) 89.9 g, acrylic acid (hereinafter also referred to as compound e-1) ) 23.5 g, 2,6-di-tert-butyl-p-cresol 0.457 g, benzyltriethylammonium chloride 0.534 g and propylene glycol-1-monomethyl ether-2-acetate 75.6 g were charged at 120 ° C. Stir for 16 hours.
The mixture was cooled to room temperature, charged with 12.0 g of 2,4-pentanedione (hereinafter also referred to as compound b-1) and 1.0 g of triethylamine, and stirred at 92 ° C. for 17 hours. After cooling to room temperature, 25.6 g of succinic anhydride (hereinafter also referred to as compound c-1), 1.39 g of tetra-n-butylammonium bromide, and 40.42 g of propylene glycol-1-monomethyl ether-2-acetate were added. Stir at 100 ° C. for 5 hours. The mixture was cooled to room temperature, 46.7 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 1 was obtained (Mw = 4090, Mn = 2630, acid value (solid content) 102 mgKOH / g).
In addition, alkali developable resin composition No. 1 is a photopolymerizable unsaturated compound (J) containing 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 2 is sandwiched between diketones in the β-diketone portion of the compound b-1 that is the component (B) Michael addition polymerization is carried out at a ratio of 0.75 or less of methylene group hydrogen atoms, and the acid anhydride structure of compound (C) as the component (C) is 0.8 at a ratio of one hydroxyl group. It was obtained by adding.

Example 2 Alkali developable resin composition No. 2 Production 9,9-bis [4- (2,3-epoxypropoxy) phenyl] -9H-fluorene (hereinafter also referred to as compound d-2) 23.2 g, acrylic acid (compound e-1) 7.35 g 2,6-di-tert-butyl-p-cresol 0.084 g, benzyltriethylammonium chloride 0.167 g and propylene glycol-1-monomethyl ether-2-acetate 20.4 g were added and stirred at 120 ° C. for 16 hours. . The mixture was cooled to room temperature, charged with 3.75 g of 2,4-pentanedione (compound b-1) and 0.304 g of triethylamine, and stirred at 92 ° C. for 17 hours. After cooling to room temperature, 7.42 g of propylene glycol-1-monomethyl ether-2-acetate was added. 5 g of this was sampled, 7.37 g of succinic anhydride (compound c-1), 0.358 g of tetra-n-butylammonium bromide, 6.35 g of propylene glycol-1-monomethyl ether-2-acetate were added at 100 ° C. Stir for 5 hours. After cooling to room temperature, 5 g of this was sampled, and 14.84 g of propylene glycol-1-monomethyl ether-2-acetate was added, and an alkali developing resin as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution Composition No. 2 was obtained (Mw = 4020, Mn = 2580, acid value (solid content) 114 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound (J) 2 contains 1.0 of the carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-2 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 2 is sandwiched between diketones in the β-diketone portion of the compound b-1 that is the component (B) Michael addition polymerization is carried out at a ratio of 0.75 or less of methylene group hydrogen atoms, and the acid anhydride structure of compound (C) as the component (C) is 0.8 at a ratio of one hydroxyl group. It was obtained by adding.

[Example 3] Alkali-developable resin composition No. Production of 3 185 g of 2,2-bis [4- (2,3-epoxypropoxy) phenyl] propane (hereinafter also referred to as compound d-3), 73.5 g of acrylic acid (compound e-1), 2,6- Di-tert-butyl-p-cresol 0.718 g, benzyltriethylammonium chloride 1.67 g and propylene glycol-1-monomethyl ether-2-acetate 174 g were charged and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 139 g of this was collected, 12.0 g of 2,4-pentanedione (Compound b-1) and 0.971 g of triethylamine were added, and the mixture was stirred at 92 ° C. for 17 hours. After cooling to room temperature, 5 g of this was sampled, and 15.5 g of succinic anhydride (compound c-1), 1.39 g of tetra-n-butylammonium bromide, and 80.8 g of propylene glycol-1-monomethyl ether-2-acetate were obtained. In addition, the mixture was stirred at 100 ° C. for 5 hours. After cooling to room temperature, the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution. 3 (Mw = 3170, Mn = 2000, acid value (solid content) 88.0 mgKOH / g).
In addition, alkali developable resin composition No. 3 includes a photopolymerizable unsaturated compound (J) having 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-3 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 2 is sandwiched between diketones in the β-diketone portion of the compound b-1 that is the component (B) Michael addition polymerization is carried out at a ratio of 0.75 or less of methylene group hydrogen atoms, and the acid anhydride structure of compound (C), which is component (C), is 0.5 per 1 hydroxyl group. It was obtained by adding.

Example 4 Alkali developable resin composition No. 4 Preparation of bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane (compound d-1) 84.3 g, acrylic acid (compound e-1) 22.1 g, 2,6 -0.429 g of di-tert-butyl-p-cresol, 0.501 g of benzyltriethylammonium chloride and 70.9 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. The mixture was cooled to room temperature, charged with 13.0 g of ethyl acetoacetate (hereinafter also referred to as compound b-2) and 0.9 g of triethylamine, and stirred at 92 ° C. for 8 hours. After cooling to room temperature, 5 g of this was sampled, and 15.0 g of succinic anhydride (compound c-1), 1.35 g of tetra-n-butylammonium bromide, and 96.9 g of propylene glycol-1-monomethyl ether-2-acetate were obtained. In addition, the mixture was stirred at 100 ° C. for 5 hours. After cooling to room temperature, the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution. 4 was obtained (Mw = 4310, Mn = 2280, acid value (solid content) 68.8 mgKOH / g).
In addition, alkali developable resin composition No. 4 includes a photopolymerizable unsaturated compound (J) having 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 5 is sandwiched between ketoesters in the β-ketoester group of the compound b-2 that is the component (B) Michael addition polymerization is carried out at a ratio of not more than 0.67 hydrogen atoms of the methylene group, and the acid anhydride structure of compound (c), which is component (C), has a ratio of 0.5 to one hydroxyl group. It was obtained by adding.

Example 5 Alkali developable resin composition No. Production of 5 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane (compound d-1) 84.3 g, acrylic acid (compound e-1) 22.1 g, 2,6 -0.429 g of di-tert-butyl-p-cresol, 0.501 g of benzyltriethylammonium chloride and 70.9 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. The mixture was cooled to room temperature, charged with 14.2 g of allyl acetoacetate (hereinafter also referred to as compound b-3) and 0.9 g of triethylamine, and stirred at 92 ° C. for 6 hours. Cool to room temperature, add 15.0 g of succinic anhydride (compound c-1), 1.35 g of tetra-n-butylammonium bromide, 96.9 g of propylene glycol-1-monomethyl ether-2-acetate and add 5 at 100 ° C. Stir for hours. After cooling to room temperature, the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution. 5 (Mw = 4870, Mn = 2440, acid value (solid content) 66.2 mgKOH / g).
In addition, alkali developable resin composition No. 5 includes a photopolymerizable unsaturated compound (J) having 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 5 is sandwiched between the ketoesters in the β-ketoester group of the compound b-3 that is the component (B) Michael addition polymerization is carried out at a ratio of not more than 0.67 hydrogen atoms of the methylene group, and the acid anhydride structure of compound (c), which is component (C), has a ratio of 0.5 to one hydroxyl group. It was obtained by adding.

[Example 6] Alkali-developable resin composition No. Preparation of 6 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane (compound d-1) 89.9 g, acrylic acid (compound e-1) 23.5 g, 2,6 -0.457 g of di-tert-butyl-p-cresol, 0.534 g of benzyltriethylammonium chloride and 75.6 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. The mixture was cooled to room temperature, charged with 12.0 g of 2,4-pentanedione (compound b-1) and 0.97 g of triethylamine, and stirred at 92 ° C. for 17 hours. After cooling to room temperature, 42.0 g of propylene glycol-1-monomethyl ether-2-acetate was added. 16.0 g of succinic anhydride (Compound c-1) was added and stirred at 100 ° C. for 5 hours. After cooling at room temperature, 5 g of this was sampled, 54.3 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution Composition No. 6 (Mw = 4210, Mn = 2630, acid value (solid content) 66.6 mgKOH / g).
In addition, alkali developable resin composition No. 6 includes a photopolymerizable unsaturated compound (J) having 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 2 is sandwiched between diketones in the β-diketone portion of the compound b-1 that is the component (B) Michael addition polymerization is carried out at a ratio of 0.75 or less of methylene group hydrogen atoms, and the acid anhydride structure of compound (C), which is component (C), is 0.5 per 1 hydroxyl group. It was obtained by adding.

[Example 7] Alkali-developable resin composition No. Production of 7 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane (Compound d-1) 89.9 g, Acrylic acid (Compound e-1) 23.5 g, 2,6 -0.457 g of di-tert-butyl-p-cresol, 0.534 g of benzyltriethylammonium chloride and 75.6 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. The mixture was cooled to room temperature, charged with 12.0 g of 2,4-pentanedione (compound b-1) and 0.97 g of triethylamine, and stirred at 92 ° C. for 17 hours. After cooling to room temperature, 42.0 g of propylene glycol-1-monomethyl ether-2-acetate was added. 24.3 g of tetrahydrophthalic anhydride (hereinafter also referred to as compound c-2) was added and stirred at 100 ° C. for 5 hours. After cooling at room temperature, 5 g of this was sampled, 67.2 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution Composition No. 7 was obtained (Mw = 4080, Mn = 2410, acid value (solid content) 62.3 mgKOH / g).
In addition, alkali developable resin composition No. 7 includes a photopolymerizable unsaturated compound (J) containing 1.0 carboxyl group of the compound e-1 as the component (E) for one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 2 is sandwiched between diketones in the β-diketone portion of the compound b-1 that is the component (B) Michael addition polymerization is carried out at a ratio of 0.75 or less of methylene group hydrogen atoms, and the acid anhydride structure of compound (C-2), which is component (C), per 0.5 hydroxyl group. It was obtained by adding.

[Example 8] Alkali-developable resin composition No. Production of 8 Addition reaction type epoxy compound of phenol and dicyclopentadiene (HP-7200H: manufactured by Dainippon Ink Co., Ltd., hereinafter also referred to as compound d-4), acrylic acid (compound e-1) 53.1 g and tetra 1.31 g of butylammonium acetate, 0.698 g of 2,6-di-tert-butyl-p-cresol and 309 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 26 hours. Cool to room temperature, 21.7 g of 2,4-pentanedione (compound b-1), 1.01 g of benzyltriethylammonium chloride, 0.276 g of 2,6-di-tert-butyl-p-cresol and propylene glycol-1 -26.5 g of monomethyl ether-2-acetate was added and stirred at 100 degrees for 9 hours. After cooling to room temperature, 15.6 g of tetrahydrophthalic anhydride (compound c-2) and 0.206 g of tetra-n-butylammonium bromide were added and stirred at 100 ° C. for 3 hours. The mixture was cooled to room temperature, 4.69 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 8 (Mw = 2850, Mn = 1660, acid value (solid content) 48.7 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound (J) contained in 8 has 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 2 is sandwiched between diketones in the β-diketone portion of the compound b-1 that is the component (B) Michael addition polymerization is carried out at a ratio of not more than 0.6 hydrogen atoms in the methylene group, and the acid anhydride structure of the compound c-2 as the component (C) is 0.8 at a ratio to one hydroxyl group. It was obtained by adding.

[Example 9] Alkali-developable resin composition No. Preparation of 9 Pentaerythritol triacrylate (hereinafter also referred to as compound a-1) 60.0 g, 2,4-pentanedione (compound b-1) 5.01 g, triphenylphosphine 0.323 g, 2,6-di- 0.0647 g of tert-butyl-p-cresol and 52.9 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 100 ° C. for 9 hours. After cooling to room temperature, 18.1 g of tetrahydrophthalic anhydride (compound c-2) and 0.323 g of tetra-n-butylammonium bromide were added and stirred at 100 ° C. for 3 hours. The mixture was cooled to room temperature, 29.9 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 9 (Mw = 1230, Mn = 690, acid value (solid content) 85.8 mgKOH / g).
In addition, alkali developable resin composition No. 9 contains a photopolymerizable unsaturated compound (J) in the β-diketone portion of the compound b-1 as the component (B) with respect to one acrylate group of the compound a-1 as the component (A). Michael addition polymerization is carried out at a ratio of 0.15 or less of methylene group hydrogen atoms sandwiched between diketones, and the acid anhydride structure of compound c-2 as component (C) is 0. It was obtained by adding 60 ratios.

[Example 10] Alkali-developable resin composition No. Preparation of 10 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane (compound d-1) 84.3 g, acrylic acid (compound e-1) 22.1 g, 2,6 -0.429 g of di-tert-butyl-p-cresol, 0.501 g of benzyltriethylammonium chloride and 70.9 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours.
The mixture was cooled to room temperature, charged with 16.2 g of 1-phenyl-1,3-butanedione (hereinafter also referred to as compound b-4) and 0.9 g of triethylamine, and stirred at 100 ° C. for 20 hours. After cooling to room temperature, 97.7 g was taken, and this was charged with 0.7 g of 1,8-diazabicyclo [5,4,0] -7-undecene and 42.36 g of propylene glycol-1-monomethyl ether-2-acetate, 100 The mixture was stirred at 17 ° C. for 17 hours and then at 120 ° C. for 23 hours. After cooling to room temperature, 7.5 g of succinic anhydride (compound c-1), 0.642 g of tetra-n-butylammonium bromide, and 8.58 g of propylene glycol-1-monomethyl ether-2-acetate were added, and the mixture was stirred at 100 ° C. for 5 hours. Stir for hours. After cooling to room temperature, the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution. 10 was obtained (Mw = 4560, Mn = 2340, acid value 66.4 (solid content) mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound (J) contained in 10 represents 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of the number is sandwiched between diketones in the β-diketone portion of the compound b-4 that is the component (B) Michael addition polymerization is carried out at a ratio of not more than 0.67 hydrogen atoms of the methylene group, and the acid anhydride structure of compound (c), which is component (C), has a ratio of 0.5 to one hydroxyl group. It was obtained by adding.

Example 11 Alkali developable resin composition No. Preparation of 11 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane (compound d-1) 84.3 g, acrylic acid (compound e-1) 22.1 g, 2,6 -0.429 g of di-tert-butyl-p-cresol, 0.501 g of benzyltriethylammonium chloride and 70.9 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours.
After cooling to room temperature, 16.3 g of 1,3-diphenyl-1,3-propanedione (hereinafter also referred to as compound b-5), 1.4 g of 1,8-diazabicyclo [5,4,0] -7-undecene And stirred at 100 ° C. for 3 hours and then at 120 ° C. for 34 hours. After cooling to room temperature, 15.0 g of succinic anhydride (compound c-1), 1.35 g of tetra-n-butylammonium bromide, and 48.9 g of propylene glycol-1-monomethyl ether-2-acetate were added, and 5 at 100 ° C. Stir for hours. After cooling to room temperature, the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution. 11 (Mw = 3590, Mn = 2250, acid value 61.0 (solid content) mgKOH / g).
In addition, alkali developable resin composition No. 11 includes a photopolymerizable unsaturated compound (J) having 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 5 is sandwiched between diketones in the β-diketone portion of the compound b-5 that is the component (B) Michael addition polymerization is carried out at a ratio of not more than 0.67 hydrogen atoms of the methylene group, and the acid anhydride structure of compound (c), which is component (C), has a ratio of 0.5 to one hydroxyl group. It was obtained by adding.

[Example 12] Alkali-developable resin composition No. Preparation of 12 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (Celoxide 2021: manufactured by Daicel Chemical Industries, Ltd., hereinafter also referred to as compound d-5), acrylic acid (compound e-1) 85 .3 g and 1.83 g of triphenylphosphine, 0.648 g of 2,6-di-tert-butyl-p-cresol and 288 g of propylene glycol-1-monomethyl ether-2-acetate were added, and the mixture was stirred at 120 ° C. for 17 hours. Cool to room temperature and add 29.6 g of 2,4-pentanedione (compound b-1), 1.90 g of tetra-n-butylammonium bromide and 0.276 g of 2,6-di-tert-butyl-p-cresol. And stirred at 100 degrees for 20 hours. After cooling to room temperature, 151 g of tetrahydrophthalic anhydride (compound c-2) and 2.34 g of tetra-n-butylammonium bromide were added and stirred at 100 ° C. for 3 hours. The mixture was cooled to room temperature, 48.3 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 12 (Mw = 1530, Mn = 930, acid value (solid content) 141 mgKOH / g).
In addition, alkali developable resin composition No. 12 includes a photopolymerizable unsaturated compound (J) having 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-5 as the component (D). One acrylate group of the epoxy adduct that is the component (A) having a structure added at a ratio of 1 to 2 is sandwiched between diketones in the β-diketone portion of the compound b-1 that is the component (B) Michael addition polymerization is carried out at a ratio of 0.5 or less of hydrogen atoms in the methylene group, and the acid anhydride structure of compound (c), component (C), is 0.8 at a ratio of one hydroxyl group. It was obtained by adding.

[Example 13] Alkaline-developable resin composition No. Production of 13 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane (compound d-1) 281 g, acrylic acid (compound e-1) 72.0 g, 2,6-di -1.43 g of tert-butyl-p-cresol, 1.67 g of benzyltriethylammonium chloride and 235 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 60.0 g of pentaerythritol tetraacrylate (hereinafter also referred to as compound a′-1), 75.0 g of 2,4-pentanedione (compound b-1) and 3.1 g of triethylamine were charged at 92 ° C. Stir for 17 hours. After cooling to room temperature, 70.0 g of succinic anhydride (compound c-1) and 4.35 g of tetra-n-butylammonium bromide were added and stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, 443 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 13 was obtained (Mw = 3770, Mn = 2300, acid value (solid content) 73 mgKOH / g).
In addition, alkali developable resin composition No. 13 includes a photopolymerizable unsaturated compound (J) having 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). (B) for one acrylate group contained in the mixture of the epoxy adduct as the component (A) and the compound a′-1 as the component (A ′) having a structure added at a ratio of ) Michael addition polymerization at a ratio of 0.75 or less of the hydrogen atoms of the methylene group sandwiched between the diketones in the β-diketone portion of compound b-1 which is the component, and further, (C) It is obtained by adding the acid anhydride structure of compound c-1 as a component at a ratio of 0.7.

[Example 14] Alkali-developable resin composition No. 14 Preparation 9,9-bis [4- (2,3-epoxypropoxy) phenyl] -9H-fluorene (compound d-2) 232.0 g, acrylic acid (compound e-1) 72.0 g, 2,6 -1.43 g of di-tert-butyl-p-cresol, 1.67 g of benzyltriethylammonium chloride and 203.0 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. The mixture was cooled to room temperature, charged with 75.0 g of 2,4-pentanedione (compound b-1), 88.0 g of pentaerythritol tetraacrylate (compound a′-1) and 3.1 g of triethylamine, and stirred at 92 ° C. for 17 hours. . After cooling to room temperature, 70.0 g of succinic anhydride (compound c-1) and 4.35 g of tetra-n-butylammonium bromide were added and stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, 415 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 14 was obtained (Mw = 3700, Mn = 2190, acid value (solid content) 79 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound (J) contained in 14 has 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-2 as the component (D). (B) for one acrylate group contained in the mixture of the epoxy adduct as the component (A) and the compound a′-1 as the component (A ′) having a structure added at a ratio of ) Michael addition polymerization at a ratio of 0.75 or less of the hydrogen atoms of the methylene group sandwiched between the diketones in the β-diketone portion of compound b-1 which is the component, and further, (C) It is obtained by adding the acid anhydride structure of compound c-1 as a component at a ratio of 0.8.

[Example 15] Alkali-developable resin composition No. Production of 15 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane (compound d-1) 281 g, acrylic acid (compound e-1) 72.0 g, 2,6-di -1.43 g of tert-butyl-p-cresol, 1.67 g of benzyltriethylammonium chloride and 235 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. Cooled to room temperature, charged with 74.0 g of trimethylolpropane triacrylate (hereinafter also referred to as compound a′-2), 75.0 g of 2,4-pentanedione (compound b-1) and 3.1 g of triethylamine, 92 ° C. For 17 hours. After cooling to room temperature, 70.0 g of succinic anhydride (compound c-1) and 4.35 g of tetra-n-butylammonium bromide were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 426 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 15 (Mw = 3650, Mn = 2220, acid value (solid content) 75 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound (J) 15 contains 1.0 carboxyl group of the compound e-1 which is the component (E) with respect to one epoxy of the compound d-1 which is the component (D). (B) for one acrylate group contained in a mixture of the epoxy adduct as the component (A) and the compound a′-2 as the component (A ′) having a structure added at a ratio of In the compound b-1, which is a component, Michael addition polymerization is carried out at a ratio of 0.86 or less of the hydrogen atoms of the methylene group sandwiched between the diketones in the β-diketone moiety, and further, for each hydroxyl group, the component (C) The acid anhydride structure of the compound c-1 is obtained by adding at a ratio of 0.7.

[Example 16] Alkali-developable resin composition No. Production of 16 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane (compound d-1) 281 g, acrylic acid (compound e-1) 72.0 g, 2,6-di -1.43 g of tert-butyl-p-cresol, 1.67 g of benzyltriethylammonium chloride and 235 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. Cooled to room temperature, charged with 145 g of tricyclodecane dimethanol diacrylate (hereinafter also referred to as compound a′-3), 75.0 g of 2,4-pentanedione (compound b-1) and 3.1 g of triethylamine, 92 ° C. For 18 hours. After cooling to room temperature, 70.0 g of succinic anhydride (compound c-1) and 4.35 g of tetra-n-butylammonium bromide were added and stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, 512 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 16 was obtained (Mw = 3780, Mn = 2450, acid value (solid content) 73 mgKOH / g).
In addition, alkali developable resin composition No. 16 includes a photopolymerizable unsaturated compound (J) having 1.0 carboxyl group of the compound e-1 as the component (E) with respect to one epoxy group of the compound d-1 as the component (D). (B) for one acrylate group contained in a mixture of the epoxy adduct as the component (A) and the compound a′-3 as the component (A ′) having a structure added at a ratio of (B) ) Michael addition polymerization at a ratio of 0.75 or less of the hydrogen atoms of the methylene group sandwiched between the diketones in the β-diketone portion of compound b-1 which is the component, and further, (C) It is obtained by adding the acid anhydride structure of compound c-1 as a component at a ratio of 0.7.

[Comparative Example 1] Alkali-developable resin composition No. Production of 17 9,9-bis [4- (2,3-epoxypropoxy) phenyl] -9H-fluorene (compound d-2) 184 g, acrylic acid (compound e-1) 58.0 g, 2,6-di -Tert-butyl-p-cresol 0.26 g, tetra-n-butylammonium bromide 0.11 g and propylene glycol-1-monomethyl ether-2-acetate 23.0 g were charged and stirred at 120 ° C. for 16 hours. Cooled to room temperature, charged with 35.0 g of propylene glycol-1-monomethyl ether-2-acetate, 59.0 biphthalic anhydride, 20.0 g tetrahydrophthalic anhydride, 0.24 g tetra-n-butylammonium bromide, The mixture was stirred at 120 ° C for 4 hours, 100 ° C for 3 hours, 80 ° C for 4 hours, 60 ° C for 6 hours, and 40 ° C for 11 hours. After cooling to room temperature, 90.0 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain a target propylene glycol-1-monomethyl ether-2-acetate solution as an alkali developable resin composition No. 17 was obtained (Mw = 5000, Mn = 2100, acid value (solid content) 93 mgKOH / g).

[Comparative Example 2] Alkali-developable resin composition No. Production of 18 2,2-bis [4- (2,3-epoxypropoxy) phenyl] propane (compound d-3) 154 g, acrylic acid (compound e-1) 59.0 g, 2,6-di-tert- 0.26 g of butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide and 23.0 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 16 hours. Cooled to room temperature, charged with 36.0 g of propylene glycol-1-monomethyl ether-2-acetate, 67.0 biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide, 120 ° C. for 4 hours, 100 ° C. For 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C. for 11 hours. After cooling to room temperature, 90.0 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain a target propylene glycol-1-monomethyl ether-2-acetate solution as an alkali developable resin composition No. 18 was obtained (Mw = 7500, Mn = 2100, acid value (solid content) 91 mgKOH / g).

[Examples 17 to 32 and Comparative Examples 3 to 4] Alkali-developable photosensitive resin composition No. Preparation of No. 1-18 Alkali developable resin composition No. obtained in Examples 1-16 and Comparative Examples 1-2. 1 to 18 g of 14 to 18, 5.0 g of pentaerythritol tetraacrylate (compound a′-1) as a monomer having an unsaturated bond and 78 g of propylene glycol-1-monomethyl ether-2-acetate as a solvent are stirred well. The alkali-developable photosensitive resin composition No. 1 of the present invention. 1-18 were obtained.

The alkali-developable photosensitive resin composition No. prepared in Examples 17 to 32 and Comparative Examples 3 to 4 was used. Evaluation of 1-18 was performed as follows.
Specifically, γ-glycidoxypropylmethylethoxysilane was spin-coated on a substrate and spin-dried well, and then the alkali-developable photosensitive resin composition was spin-coated (1300 rpm) for 50 seconds and dried. I let you. After pre-baking at 70 ° C. for 20 minutes, a 5% by mass polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, exposure was performed using a predetermined mask and an ultrahigh pressure mercury lamp as a light source so that the exposure amount was 150 mJ / cm ² . Thereafter, the film was developed by being immersed in a 2.5% by mass sodium carbonate solution at 25 ° C. for 30 seconds, and thoroughly washed with water.
At this time, a pattern was formed as ◯, and a pattern was not formed as x. The results are shown in Table 1.

The alkali-developable photosensitive resin compositions of Examples 17 to 32 were cured by exposure without a photopolymerization initiator (F), and a pattern was formed by alkali development.
On the other hand, the alkali-developable photosensitive resin compositions of Comparative Examples 3 to 4 did not cure even when exposed without the photopolymerization initiator (F), and a pattern could not be formed by alkali development.

[Examples 33 to 48 and Comparative Examples 5 to 6] Alkali-developable photosensitive resin composition No. Preparation of 19-36 Alkali developable resin composition No. obtained in Examples 1-16 and Comparative Examples 1-2. 1 to 18 of 14 g, trimethylolpropane triacrylate (compound a′-2) 6.0 g as a monomer having an unsaturated bond, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator (F) 3.0 g of propylene glycol-1-monomethyl ether-2-acetate as a solvent and 78 g of the solvent were added and well stirred, and the alkali-developable photosensitive resin composition no. 19-36 were obtained.

The alkali-developable photosensitive resin composition No. prepared in Examples 33 to 48 and Comparative Examples 5 to 6 were used. Evaluation of 19-36 was performed as follows.
Specifically, γ-glycidoxypropylmethylethoxysilane was spin-coated on a substrate and spin-dried well, and then the alkali-developable photosensitive resin composition was spin-coated (1300 rpm) for 50 seconds and dried. I let you. After pre-baking at 70 ° C. for 20 minutes, a 5% by mass polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, the film was exposed using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, then developed by immersing in a 2.5% by weight sodium carbonate solution at 25 ° C. for 30 seconds, and thoroughly washed with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. The following evaluation was performed about the obtained pattern. The results are shown in Table 2.

<Sensitivity>
During exposure, what exposure was sufficient 100 mJ / cm ² a, insufficient in 100 mJ / cm ^2, a material obtained by exposing at 150 mJ / cm ² b, insufficient in 150mJ / cm ^2, 200mJ / cm ^The one exposed in ² was designated as c.
<Resolution>
At the time of exposure and development, A is good pattern formation even if the line width is 10 μm or less, B is good pattern formation if the line width is 10 to 30 μm, and good pattern formation is required unless the line width is 30 μm or more. What was not made was evaluated as C.
<Adhesion>
The pattern obtained by development was observed for peeling. The pattern in which no peeling was observed was marked with ◯, and the pattern in which peeling was observed was marked with x.

The alkali-developable photosensitive resin compositions of Examples 33 to 48 had high sensitivity and excellent resolution. Moreover, it was excellent in adhesiveness with the substrate and had little pattern peeling.
On the other hand, the alkali-developable photosensitive resin compositions of Comparative Examples 5 to 6 were low in sensitivity and low in resolution and adhesion to the substrate.

[Examples 49 to 64 and Comparative Examples 7 to 8] Colored alkali-developable photosensitive resin composition No. Preparation of No. 1-18 Alkali developable resin composition No. obtained in Examples 1-16 and Comparative Examples 1-2. 1 to 18 of 44 g, 10.0 g of pentaerythritol tetraacrylate (compound a′-1) as a monomer having an unsaturated bond, and 2-methyl-1- (4-methylthiophenyl) as a photopolymerization initiator (F) 2-morpholinopropan-1-one (Irg907) 5.0 g, carbon black (“MA100” manufactured by Mitsubishi Chemical Co., Ltd.) 19 g as a coloring material (G) and propylene glycol-1-monomethyl ether-2-acetate 75 g as a solvent In addition, the mixture is well stirred and the colored alkali-developable photosensitive resin composition No. 1-18 were obtained.

The colored alkali-developable photosensitive resin composition Nos. Prepared in Examples 49 to 64 and Comparative Examples 7 to 8 were used. Evaluation of 1-18 was performed as follows.
Specifically, γ-glycidoxypropylmethylethoxysilane was spin-coated on a substrate and spin-dried well, and then the colored alkali-developable photosensitive resin composition was spin-coated (1300 rpm) for 50 seconds. Dried. After pre-baking at 70 ° C. for 20 minutes, a 5% by mass polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, the film was exposed using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, then developed by immersing in a 2.5% by weight sodium carbonate solution at 25 ° C. for 30 seconds, and thoroughly washed with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. The following evaluation was performed about the obtained pattern. The results are shown in Table 1.

<Sensitivity>
During exposure, what exposure was sufficient 70 mJ / cm ² a, inadequate in 70 mJ / cm ^2, a material obtained by exposing at 100 mJ / cm ² b, insufficient in 100mJ / cm ^2, 150mJ / cm ^The one exposed in ² was designated as c.
<Resolution>
At the time of exposure and development, a pattern that can be satisfactorily formed even if the line width is 8 μm or less is A, a pattern that can be satisfactorily formed if the line width is 10 to 30 μm, B, and a pattern that is good if the line width is not 30 μm or more. What was not made was evaluated as C.
<Adhesion>
The pattern obtained by development was observed for peeling. The pattern in which no peeling was observed was marked with ◯, and the pattern in which peeling was observed was marked with x.

The alkali-developable photosensitive resin compositions of Examples 49 to 64 had high sensitivity and excellent resolution. Moreover, it was excellent in adhesiveness with the substrate and had little pattern peeling.
On the other hand, the alkali-developable photosensitive resin compositions of Comparative Examples 7 to 8 were low in sensitivity and low in resolution and adhesion to the substrate.

Claims (6)

  A hydroxyl group of a reaction product obtained by adding a compound having a β-diketone group or a compound having a β-ketoester group to a (meth) acryloyl group of a compound having two or more (meth) acryloyl groups and a hydroxyl group; An alkali-developable photosensitive resin composition comprising a photopolymerizable unsaturated compound having a structure obtained by an esterification reaction with a polybasic acid anhydride.   2. The alkali-developable photosensitive resin composition according to claim 1, wherein the compound having two or more (meth) acryloyl groups and a hydroxyl group has a structure which is a reaction product obtained by adding an unsaturated monobasic acid to an epoxy compound. . The alkali-developable photosensitive resin composition according to claim 2, wherein the epoxy compound has a structure represented by the following general formula (I).

(In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a hydrogen atom, a phenyl group or a cycloalkyl group having 3 to 10 carbon atoms, and the phenyl group and the cycloalkyl group are carbon atoms. The alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms or the halogen atom may be substituted, and Y and Z are each independently an alkyl group having 1 to 10 carbon atoms and 1 carbon atom. Represents an alkoxy group having 10 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom, the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and n represents a number from 0 to 10; P and r each independently represent a number of 0 to 4.)   The alkali-developable photosensitive resin composition according to claim 3, wherein, in the general formula (I), Cy is a cyclohexyl group, X is a phenyl group, and p and r are 0.   Furthermore, the photopolymerization initiator is contained, The alkali developable photosensitive resin composition in any one of Claims 1-4.   A colored alkali-developable photosensitive resin composition obtained by further adding a colorant to the alkali-developable photosensitive resin composition according to claim 1.