TWI416254B - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition, a pattern formed by using the composition, and a display device containing the pattern are provided to improve storage stability, pattern shape, surface smoothness, mechanical properties, heat resistance and solvent resistance. A photosensitive resin composition comprises a binder resin which is a copolymer of (A1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, (A2) an aliphatic polycyclic epoxy compound and (A3) a monomer different from (A1) and (A2) and polymerizable with (A1) and (A2); a photopolymerizable compound which contains a compound having an unsaturated double bond equivalence of 120-400 g/eq; a photopolymerization initiator; and a solvent. Preferably the compound having an unsaturated double bond equivalence of 120-400 g/eq is represented by the formula (BA).

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition.

A spacer is provided between the filter plate constituting the display device and the array substrate, such as a liquid crystal display device or a touch panel, in order to maintain the interval between the two substrates. Spherical particles such as glass beads, plastic beads, etc. are used for this spacer.

However, if such a spherical particle is used, since the spherical particle is scattered disorderly on the glass substrate, the TFT element or the electrode may be damaged, and if the spherical particle exists in the penetrating pixel portion, it is incident. The scattering of light has a situation in which the contrast of the liquid crystal display element is lowered. Thus, there has been proposed to use a photosensitive resin composition instead of using spherical particles to form a spacer. According to this method, spacers can be formed at any place, so that the aforementioned problems can be solved.

As such a photosensitive resin composition, an acrylic copolymer having a carboxyl group and a glycidyl ether group as a binder resin and dipentaerythritol hexaacrylate as a photopolymerizable compound (Japanese chemical) are known. A composition of KAYARAD DPHA and an unsaturated double bond binding equivalent: 105 g/eq) (refer to Patent Document 1), and discloses that solvent resistance can be obtained by using the composition to form a spacer pattern. A spacer pattern excellent in heat resistance.

[Patent Document 1] JP-A-11-133600

However, when the photosensitive resin composition is used to form a pattern of a spacer on a transparent conductive film such as ITO (indium-tin oxide), if a fine pattern is formed, development and water washing processes are known. The problem that the pattern is peeled off and the surface smoothness is lowered.

An object of the present invention is to provide a photosensitive resin composition which can form a fine line width pattern even on a transparent conductive film such as ITO (indium-tin oxide).

The inventors of the present invention have reviewed the photosensitive resin composition capable of solving the above-mentioned problems, and found that a photosensitive resin composition containing a photopolymerizable compound having a certain range of unsaturated double bond binding equivalents can form a fine line width. pattern.

That is, the present invention provides the following [1] to [5].

[1] A photosensitive resin composition comprising a photosensitive resin composition comprising a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D), wherein The binder resin (A) is an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (A1), and an aliphatic polyvalent epoxy compound (A2), and is different from (A1) and (A2) and is compatible with A1) and (A2) a copolymer of the monomer (A3) copolymerized, and the photopolymerizable compound (B) contains a compound having an unsaturated double bond binding equivalent of from 120 to 400 g/eq.

[2] The photosensitive resin composition according to [1], wherein the compound having an unsaturated double bond binding equivalent of from 120 to 400 g/eq is a compound represented by the formula (BA).

In the formula (BA), R ^a to R ^f each independently represent a hydrogen atom or a group represented by the formula (BA-1) to (BA-3),

At least four groups of R ^a to R ^{f are} at least one group represented by formula (BA-1) to (BA-3), and at least one group of R ^a to R ^f is represented by formula (BA-2) or The formula (BA-3) represents the basis. ]

[3] The photosensitive resin composition according to [1] or [2] wherein the aliphatic polycyclic epoxy group monomer (A2) has a compound selected from the group consisting of the formula (I) And at least one compound selected from the group consisting of compounds represented by formula (II).

In the formulae (I) and (II), each of the R groups independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, and the X system each independently represents a single bond or a hetero atom. It can also be an alkyl group having a carbon number of 1 to 6. ]

[4] A pattern formed by using the photosensitive resin composition as described in [1] to [3].

[5] A display device comprising the pattern described in [4].

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention contains a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D). In the photosensitive resin composition of the present invention, usually, the binder resin (A), the photopolymerizable compound (B), and the photopolymerization initiator (C), and any other additives (F) are dissolved or Dispersed in solvent (D). The photosensitive resin composition of the present invention is preferably used as a pattern forming material.

The binder resin (A) used in the present invention is an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride (A1), an aliphatic polycyclic epoxy compound (A2), and is different from (A1) and (A2). And a copolymer of the monomer (A3) copolymerizable with (A1) and (A2). The binder resin (A) is preferably one having an alkali solubility.

Specific examples of the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride (A1) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid and fumaric acid; An unsaturated dicarboxylic acid such as citric acid, mesaconic acid or itaconic acid; and an acid anhydride of the above unsaturated dicarboxylic acid; succinic acid mono [2-(methyl) propylene oxyethyl] ester, benzene An unsaturated mono[(methyl)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid having a divalent or higher valence of mono-[2-(methyl)acryloyloxyethyl]ester or the like; such as α-(hydroxyl) An acrylate-like unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are suitably used because of their copolymerization reactivity and solubility in an alkaline aqueous solution. These may be used alone or in combination of two or more.

The above aliphatic polycyclic epoxy compound (A2) is a cyclic epoxy group compound of an aliphatic polycyclic compound, and the above aliphatic polycyclic epoxy compound (A2) is aliphatic. It is preferred that the polycyclic compound has an epoxy group and a compound having an unsaturated bond. The aliphatic polycyclic compound may, for example, be dicyclopentane or tricyclodecane.

The aliphatic polycyclic epoxy compound (A2) is preferably a compound which is preferably at least one selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II).

In the formulae (I) and (II), R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group.

The X-forms each independently represent a single bond or a heteroalkyl group having a carbon number of 1 to 6.

Specific examples of R include an alkyl group of a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a t-butyl group; a hydroxymethyl group; Hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxy-isopropyl, 2-hydroxy-isopropyl, A hydroxyl group-containing alkyl group such as 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl or the like. Among them, a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group or a 2-hydroxyethyl group are preferable, and a hydrogen atom or a methyl group is preferable.

In the case of X, specifically, a single bond; an alkylene group such as a methylene group, an ethylidene group, or a propyl group; an oxymethylene group, an oxygen-extended ethyl group, an oxygen-extension propyl group, and a thiomethylene group; And a sulfur-extended ethyl group, a sulfur-extension propyl group, an aminomethylene group, an amine-based ethyl group, an amine-based propyl group, and the like, and a hetero atom-containing alkyl group. Among them, a single bond, a methylene group, an ethylidene group, an oxymethylene group, and an oxygen-extended ethyl group are preferable, and a single bond or an oxygen-extended ethyl group is preferable.

The compound represented by the formula (I), for example, a compound represented by the formula (I-1) to the formula (I-15), and the like, and a formula (I-1) and a formula (I-3) are preferable. , formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), preferably, formula (I-1), formula (I-7), formula (I-9), and formula (I-15).

Examples of the compound represented by the formula (II) include a compound represented by the formula (II-1) to the formula (II-15), and those of the formula (II-1) and (II-3) are preferred. , formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), preferably, formula (II-1), formula (II-7), formula (II-9), and formula (II-15).

At least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in any ratio. In the case of mixing, the mixing ratio is in molar ratio, and is preferably (I): Formula (II) is 5:95 to 95:5, preferably 10:90 to 90:10, more preferably 20: 80~80:20.

The monomer (A3) which is different from the above (A1) and (A2) and which can be copolymerized with (A1) and (A2) may, for example, be methyl (meth)acrylate or (methyl). Ethyl acrylate, n-butyl (meth)acrylate, dibutyl (meth)acrylate, tert-butyl (meth)acrylate, etc.; alkyl acrylate, acrylic acid alkyl esters of acrylic acid and propyl; (meth) acrylate, (meth) acrylate, 2-methyl-cyclohexyl ester, (meth) acrylate, tricyclo [5.2.1.0 ^2.6] dec-8-yl An ester (referred to as dicyclopentyl (meth) acrylate as a conventional name in the technical field), dicyclopentyloxy (meth)acrylate, isodecyl (meth)acrylate, etc. (methyl) Cyclic alkyl acrylates; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2.6 ] 癸-8-yl acrylate (known in the art as dicyclopentyl acrylate) The ester is a conventional name.), a cyclic alkyl alkyl acrylate such as dicyclopentaoxyethyl acrylate or isodecyl acrylate; (meth) phenyl (meth) acrylate or benzyl (meth) acrylate Acrylic acid aromatic esters; acrylic acid benzene Acrylic acid aromatic esters such as benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; 2-hydroxyethyl (meth)acrylate, a hydroxyalkyl ester such as 2-hydroxypropyl (meth)acrylate; bicyclo[2,2,1]hept-2-ene, 5-methylbicyclo[2,2,1]hept-2-ene, 5-ethylbicyclo[2,2,1]hept-2-ene, 5-hydroxybicyclo[2,2,1]hept-2-ene, 5-carboxybicyclo[2,2,1]hept-2- Alkene, 5-hydroxymethylbicyclo[2,2,1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2,2,1]hept-2-ene, 5-methoxy Bicyclo[2,2,1]hept-2-ene, 5-ethoxybicyclo[2,2,1]hept-2-ene, 5,6-dihydroxybicyclo[2,2,1]hept-2 - alkene, 5,6-dicarboxybicyclo[2,2,1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2,2,1]hept-2-ene, 5,6 -bis(2'-hydroxyethyl)bicyclo[2,2,1]hept-2-ene, 5,6-dimethoxybicyclo[2,2,1]hept-2-ene, 5,6- Diethoxybicyclo[2,2,1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2,2,1]hept-2-ene, 5-hydroxy-5-ylbicyclo[2 , 2,1]hept-2-ene, 5-carboxy-5-methylbicyclo[2,2,1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2,2,1]g 2-ene, 5-ylmethyl-5-methylbicyclo[2,2,1]hept-2-ene, 5-carboxy-6-methyl Ring [2,2,1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2,2,1]hept-2-ene, dehydrated 5,6-dicarboxybicyclo[2,2,1 Hept-2-ene (Hamimic anhydride), 5-t-butoxycarbonylbicyclo[2,2,1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2,2,1] Hept-2-ene, 5-carboxybicyclo[2,2,1]hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[2,2,1]hept-2-ene, a bicyclic unsaturated compound of 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2,2,1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmalanium Imine, N-benzyl maleimide, benzoic acid N-succinic acid imino-3-maleimide, butyric acid N-succinic acid imino-4-merine Amine ester, decanoic acid N-succinate, imidate-6-maleimide, propionate N-succinate, imidate-3-maleimide, N-(9-acridine Dicarbonyl quinone imine derivatives such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy Styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, decylamine, methacrylamide, vinyl acetate, 1,3-butadiene, different Diene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, α-n-propyl acrylate ring Oxypropyl propyl ester, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl epoxy propyl ether, m-vinylbenzyl epoxy propyl ether, P-vinylbenzyl epoxypropyl ether or the like.

Among these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene It is preferable to consider the copolymerization reactivity and the solubility in an alkaline aqueous solution. These may be used alone or in combination of two or more.

The binder resin (A) used in the present invention is a copolymer obtained by copolymerizing (A1), (A2) and (A3), and the ratio of the constituent components derived from each of them is relative to the constitution The molar fraction of the total number of moles of the constituent components of the copolymer is preferably in the range of the following.

The constituent unit derived from (A1); 2~40 mol% The constituent unit derived from (A2); 2~95 mol% The constituent unit derived from (A3); 1~65 mol%

Further, it is preferred that the ratio of the above-mentioned constituent components is in the following range.

The constituent unit derived from (A1); 5~35 mol% The constituent unit derived from (A2); 5~80 mol% The constituent unit derived from (A3); 1~60 mol%

When the composition ratio is within the above range, the storage stability of the photosensitive resin composition, the developability of the pattern obtained from the composition, the solvent resistance, the heat resistance, and the mechanical strength tend to be good.

The above-mentioned binder resin (A) can be referred to, for example, the document "Experimental method for polymer synthesis" (published by Otsuka Ryokan, Ltd., Chemical Co., Ltd., 1st edition, 1st brush, issued on March 1, 1972). The method and the cited documents described in the literature were produced.

Specifically, a compound which quantitatively derivates the units (A1), (A2), and (A3) constituting the copolymer, a polymerization initiator, and a solvent are charged into a reaction vessel, and nitrogen is substituted by oxygen. The polymer can be obtained by stirring, heating, and keeping warm in the absence of oxygen. Further, the obtained copolymer may be used as it is, and may be used as a concentrated or diluted solution, and may be used by removing the solid (powder) by reprecipitation or the like.

The polystyrene-equivalent weight average molecular weight of the above-mentioned binder resin (A) is preferably from 3,000 to 100,000, preferably from 5,000 to 50,000. When the weight average molecular weight of the binder resin (A) is in the above range, coating properties tend to be good, and film loss is unlikely to occur during development, and the non-pixel portion is removed during development. There is a good tendency, so it is better.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A) is preferably from 1.1 to 6.0, preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, it is preferred because it has a high affinity for development.

The content of the binder resin (A) used in the photosensitive resin composition of the present invention is relative to the solid matter in the photosensitive resin composition (meaning that the composition in the composition is solid at 25 ° C) The mass fraction is preferably from 5 to 90% by mass, preferably from 10 to 70% by mass. When the content of the binder resin (A) is within the above range, the solubility in the developing solution is sufficient, and it is difficult to develop the residue on the substrate of the non-pixel portion, and the exposed portion is formed at the time of development. The membrane loss of the pixel part is difficult to occur, the non-pixel part The removal property is a good tendency, so it is preferable.

The photopolymerizable compound (B) used in the present invention contains a compound having an unsaturated double bond binding equivalent of from 120 to 400 g/eq. In the case of a compound having an unsaturated double bond binding equivalent of from 120 to 400 g/eq, a compound represented by the formula (BA) is suitably used.

In the formula (BA), R ^a to R ^f are each independently a hydrogen atom or a group represented by the formula (BA-1) to (BA-3).

However, at least four of R ^a to R ^{f are} represented by any one of formulas (BA-1) to (BA-3), and at least one of R ^a to R ^f is represented by formula (BA-2) or The formula (BA-3) represents the basis.

In the case of the compound represented by the formula (BA), R ^a to R ^f are preferable, two are hydrogen atoms, three are represented by the formula (BA-1), and one is a formula (BA). -2) a compound represented by a group; two are a hydrogen atom, three are a group represented by the formula (BA-1), and one is a compound represented by the formula (BA-3); two are hydrogen atoms Two are compounds represented by the formula (BA-1), and two are compounds represented by the formula (BA-2); two are hydrogen atoms; and two are represented by the formula (BA-1) One is a compound represented by the formula (BA-2), and the other is a compound represented by the formula (BA-3); two are hydrogen atoms; and two are represented by the formula (BA-1). 2 are compounds represented by the formula (BA-3); 2 are hydrogen atoms, 1 is a group represented by the formula (BA-1), and 3 are groups represented by the formula (BA-2) a compound; two are hydrogen atoms, one is a group represented by the formula (BA-1), two are a group represented by the formula (BA-2), and one is a group represented by the formula (BA-3). a compound; two are hydrogen atoms, one is a group represented by the formula (BA-1), one is a group represented by the formula (BA-2), and two are groups represented by the formula (BA-3). a compound; two are hydrogen atoms and one is a formula (BA-1) 3, 3 are compounds represented by the formula (BA-3); 2 are hydrogen atoms, 4 are compounds represented by the formula (BA-2); 2 are hydrogen atoms, 3 are a group represented by the formula (BA-2), one of which is a compound represented by the formula (BA-3); two of which are hydrogen atoms, two of which are represented by the formula (BA-2), and two of which are a compound represented by the formula (BA-3); two of which are a hydrogen atom, one of which is a group represented by the formula (BA-2), and three are a group represented by the formula (BA-3); a hydrogen atom and four compounds represented by the formula (BA-3); one is a hydrogen atom; four are represented by the formula (BA-1); and one is represented by the formula (BA-2). a compound represented by a group; one is a hydrogen atom, four are a group represented by the formula (BA-1), and one is a compound represented by the formula (BA-3); one is a hydrogen atom, and three are a compound represented by the formula (BA-1) and two compounds represented by the formula (BA-2); one is a hydrogen atom; three are a group represented by the formula (BA-1), and one is a compound represented by the formula (BA-2) and one compound represented by the formula (BA-3); one is a hydrogen atom, three are a group represented by the formula (BA-1), and two are For the combination of the formula (BA-3) One compound is a hydrogen atom, two are a group represented by the formula (BA-1), and three are compounds represented by the formula (BA-2); one is a hydrogen atom; two are a formula ( The group represented by BA-1), two of which are represented by the formula (BA-2), and one of which is a group represented by (BA-3); one is a hydrogen atom and two are a formula (BA) -1) a group represented by a group represented by the formula (BA-2) and two compounds represented by the formula (BA-3); one is a hydrogen atom and two are a formula (BA) -1) indicates a group, and three of them are compounds represented by the formula (BA-3); one is a hydrogen atom, one is a group represented by the formula (BA-1), and four are a formula (BA). -2) a compound represented by a group; one is a hydrogen atom, one is a group represented by the formula (BA-1), three is a group represented by the formula (BA-2), and one is a formula (BA) -3) a compound represented by a group; one is a hydrogen atom, one is a group represented by the formula (BA-1), two is a group represented by the formula (BA-2), and two are a formula (BA) -3) a compound represented by a group; one is a hydrogen atom, one is a group represented by the formula (BA-1), one is a group represented by the formula (BA-2), and three are a formula (BA). -3) a compound represented by a group; one is a hydrogen atom and one is a formula (BA) -1) a compound represented by a group represented by the formula (BA-3); one of which is a hydrogen atom; five of which are a group represented by the formula (BA-2); and one of which is a hydrogen atom Four are compounds represented by the formula (BA-2), and one is a compound represented by the formula (BA-3); one is a hydrogen atom and three are a group represented by the formula (BA-2); Two are compounds represented by the formula (BA-3); one is a hydrogen atom, two are a group represented by the formula (BA-2), and three are a group represented by (BA-3). a compound; one is a hydrogen atom, one is a group represented by the formula (BA-2), and four are compounds represented by (BA-3); one is a hydrogen atom; and five are a formula (BA) -3) a compound represented by a group; 5 are a compound represented by the formula (BA-1), and 1 is a compound represented by the formula (BA-2); and 5 are represented by the formula (BA-1) a compound which is a group represented by the formula (BA-3); four are compounds represented by the formula (BA-1), and two are compounds represented by the formula (BA-2); One is a group represented by formula (BA-1), one is a group represented by formula (BA-2), and one is a compound represented by formula (BA-3); four are formulas (BA) -1) indicates the basis and 2 are expressed by the formula (BA-3). a compound of the formula; 3 are compounds represented by the formula (BA-1), 3 are compounds represented by the formula (BA-2); 3 are groups represented by the formula (BA-1), 2 It is a compound represented by the formula (BA-2), and one is a compound represented by the formula (BA-3); three are represented by the formula (BA-1), and one is represented by the formula (BA-). 2) a group represented by two, a compound represented by the formula (BA-3); three of which are represented by the formula (BA-1), and three of which are represented by the formula (BA-3) a compound; two are compounds represented by the formula (BA-1), four are compounds represented by the formula (BA-2); two are represented by the formula (BA-1), and three are A compound represented by the formula (BA-2), one of which is a group represented by (BA-3); two of which are represented by the formula (BA-1), and two of which are represented by the formula (BA-2) The two groups are compounds represented by the formula (BA-3); two are groups represented by the formula (BA-1), one is a group represented by the formula (BA-2), and three are a compound represented by the formula (BA-3); two are compounds represented by the formula (BA-1), four are compounds represented by the formula (BA-3); and one is a formula (BA) -1) indicates a group, and 5 are compounds represented by the formula (BA-2); BA-1) represents a group, four are compounds represented by formula (BA-2), and one is a compound represented by formula (BA-3); one is represented by formula (BA-1) The base is a compound represented by the formula (BA-2), and two are compounds represented by the formula (BA-3); one is a group represented by the formula (BA-1), and two are The formula (BA-2) represents a group, and the three are compounds represented by the formula (BA-3); one is represented by the formula (BA-1), and one is represented by the formula (BA-2). a compound represented by the formula, wherein the four are compounds represented by the formula (BA-3); one is a group represented by the formula (BA-1), and five are compounds represented by the formula (BA-3); 6 are compounds represented by the formula (BA-2); 5 are compounds represented by the formula (BA-2), and 1 is a compound represented by the formula (BA-3); The formula (BA-2) represents a group, two of which are compounds represented by the formula (BA-3); three are represented by the formula (BA-2), and three are of the formula (BA-3) a compound represented by the formula; 2 are a compound represented by the formula (BA-2), 4 are compounds represented by the formula (BA-3); and 1 is a group represented by the formula (BA-2), 5 are compounds represented by the formula (BA-3); 6 are represented by (BA-3) Thereof and the like.

Among them, a compound having an unsaturated double bond binding equivalent of 200 to 350 g/eq is particularly preferable, and as the compound, a compound having 6 groups represented by the formula (BA-2) and 6 compounds can be cited. The base is a compound represented by the formula (BA-3).

Examples of the compound represented by the formula (BA) include R ^a to R ^f , two of which are KAYARAD DPCA-20 of the compound represented by the formula (BA-2), and three of which are of the formula (BA-2). KAYARAD DPCA-30 of the compound represented by the formula, KAYARAD DPCA-60 of the compound represented by the formula (BA-2), and KAYARAD DPCA-120 of the compound represented by the formula (BA-3) All of them are marketed by Nippon Kayaku Co., Ltd.).

The photopolymerizable compound other than the compound represented by the formula (BA) contained in the photopolymerizable compound (B) may, for example, be a trifunctional or higher polyfunctional monomer.

Specific examples of the polyfunctional monomer having a trifunctional or higher functional group include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and a reaction product of pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri(meth) acrylate and an acid anhydride, dipentaerythritol penta (meth) acrylate and an acid anhydride, and the like. Among them, a polyfunctional monomer having a tetrafunctional group or more is particularly suitable for use. These photopolymerizable compounds may be used singly or in combination of two or more kinds.

The content of the photopolymerizable compound (B) is preferably from 1 to 70% by mass, preferably from 5 to 60% by mass based on the total mass of the binder resin (A) and the photopolymerizable compound (B). %. When the content of the photopolymerizable compound (B) is within the above range, the strength, smoothness, and reliability of the pixel portion tend to be good, which is preferable.

In addition, the content of the compound represented by the formula (BA) is usually a mass fraction based on the total amount of the compound represented by the formula (BA) and the photopolymerizable compound other than the compound represented by the formula (BA), usually It is 3 to 100% by mass, preferably 3 to 70% by mass, preferably 3 to 50% by mass, more preferably 5 to 40% by mass. The content of the compound represented by the formula (BA), if in the foregoing In addition, since the balance between sensitivity and image adhesion is a good tendency, it is preferable.

The photopolymerization initiator (C) contained in the photosensitive resin composition of the present invention may, for example, be an acetophenone-based, a diimidazole-based, an anthraquinone-based, a triazine-based or a phosphine oxide-based initiator. Since the photopolymerization initiator (C) is used in combination with the photopolymerization initiator (C-1), the photosensitive resin composition obtained has a higher sensitivity, and if a pattern is formed using the article, The productivity of the pattern is improved, so it is better.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2- Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methyl sulphate Phenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-(2-A Benzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4- Morpholinylphenyl)-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-ethyl Benzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4-? Phenylphenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2,3-di Methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-dimethylamino-1 -(4-morpholinylphenyl)-butanone, 2-(2-chlorobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2 -bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3- Benzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-morpholine Phenylphenyl)- Butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamine 1-(4-morpholinylphenyl)-butanone, 2-(2-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone , 2-(3-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(4-methoxybenzyl)-2-di Methylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methyl-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholine Phenylphenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2- Bromo-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-hydroxy-2-methyl-1-[4-(1- An oligomer of methylvinyl)phenyl]propan-1-one or the like.

The above-mentioned biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis (2) (3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, JP-A-6-75372, JP-A-6-75373, etc.), 2, 2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -tetrakis(alkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)bisimidazole, 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62- In the case of 174204, etc., the imidazole compound in which the phenyl group at the 4,4'5,5' position is substituted with an alkoxycarbonyl group (for example, see JP-A-7-10913, etc.), etc., is preferably 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4', 5,5'-tetraphenylbisimidazole.

The above-mentioned hydrazine compound may, for example, be o-ethoxycarbonyl-α- Mercapto-1-phenylpropan-1-one, a compound represented by the formula (3), a compound represented by the formula (4), and the like.

The above-mentioned triazine-based compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-double. (trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5 -triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2 -yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5- Triazine and the like.

The above-mentioned cerium oxide phosphine-based initiator may, for example, be oxidized 2,4,6-trimethylbenzimidyldiphenylphosphine.

Further, as long as the effects of the present invention are not impaired, a photopolymerization initiator or the like which is generally used in the field can be used in combination. The photopolymerization initiator may, for example, be a benzoin compound, a benzophenone compound, a thioxanthone compound or an onion compound.

More specifically, the following compounds may be mentioned, and these may be used alone or in combination of two or more.

The benzoin-based compound may, for example, be benzoin or benzene. Alanine methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzylidene benzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenyl. Thiol, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the aforementioned thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxene. Ketone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the onion-based compound include 9,10-dimethoxy onion, 2-ethyl-9,10-dimethoxy onion, 9,10-diethoxy onion, and 2-ethyl. -9,10-diethoxy onion, etc.

Others are also 10-butyl-2-chloroacridone, 2-ethyl onion, diphenylethylenedione, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene A compound or the like is exemplified as a photopolymerization initiator.

Further, as a photopolymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-A-2002-544205 can be used.

The photopolymerization initiator having the above-mentioned group capable of causing chain transfer may, for example, be a photopolymerization initiator of the formulae (5) to (10).

The photopolymerization initiator having the above-mentioned group capable of causing chain transfer can also be used as the constituent component (A3) of the above copolymer. Further, as the obtained copolymer, a binder resin which is a photosensitive resin composition of the present invention can be used, and it can also be used in combination with a binder resin.

Further, the photopolymerization initiator may be used in combination with a photopolymerization initiation aid (C-1). As the photopolymerization initiation aid, an amine compound and a carboxylic acid compound are suitably used, and an aromatic amine compound is suitably used as the amine compound.

Specific examples of the photopolymerization initiation aid include an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine, methyl 4-dimethylaminobenzoate, and 4-dimethyl group. Ethyl benzoic acid ethyl ester, 4-dimethylamino benzoic acid isoamyl ester, 4-dimethylamino benzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylaminoethyl ester, N, N-di Aromatic amines such as methyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (generalized as: miconesone), 4,4'-bis(diethylamino)benzophenone Compound.

Examples of the carboxylic acid compound include benzenesulfonic acid, methylbenzenesulfonic acid, ethylbenzenesulfonic acid, methylethylbenzenesulfonic acid, dimethylbenzenesulfonic acid, and methoxybenzenesulfonic acid. Aromatic compounds such as dimethoxybenzenesulfonic acid, chlorobenzenesulfonic acid, dichlorobenzenesulfonic acid, N-phenylglycine, phenoxyacetic acid, naphthalenesulfonic acid, N-naphthylglycine, naphthyloxyacetic acid, etc. Miscellaneous acetic acid.

The content of the photopolymerization initiator (C) is expressed by mass fraction with respect to the total amount of the binder resin (A) and the photopolymerizable compound (B), and is preferably from 0.1 to 40% by mass, preferably from 1 to 2. 30% by mass.

Further, the content of the photopolymerization initiation aid (C-1) is preferably from 0.01 to 50% by mass, preferably from 0.1 to 40% by mass, based on the same criteria as described above.

When the total amount of the photopolymerization initiator (C) is within the above range, if the photosensitive resin composition is highly sensitive, the intensity of the pixel portion formed by the above-mentioned photosensitive resin composition or the aforementioned pixel can be used. The smoothness of the surface tends to be good, so it is preferable. When the amount of the photopolymerization initiation aid (C-1) is within the above range, the sensitivity of the obtained photosensitive resin composition is further increased, and the photosensitive resin composition is used. The productivity of the pattern substrate is preferably improved.

The solvent (D) which can be used in the present invention includes various organic solvents which are generally used in the field of photosensitive resin compositions.

Specific examples of the solvent (D) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; methyl cellosolve acetate, acetic acid Glycol alkyl ether acetate such as ethyl cellosolve; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, acetic acid Alkyl glycol alkyl ether acetates such as oxyamyl ester; aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene; methyl ethyl ketone, acetone, methyl ketone, methyl isobutyl ketone, cyclohexanone Ketones; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, etc.; ethyl 3-ethoxypropionate, 3-methoxypropionic acid An ester such as an ester; a cyclic ester such as γ-butyrolactone;

Among the above-mentioned solvents, from the viewpoints of applicability and drying properties, an organic solvent having a boiling point of 100 ° C to 200 ° C in the solvent is preferable, and an alkylene glycol alkyl ether is preferred. Esters such as acetates, ketones, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc., more preferably Examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.

These solvents (D) may be used alone or in combination of two or more.

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably from 60 to 90% by mass, preferably from 70 to 85% by mass, based on the mass fraction of the photosensitive resin composition. The content of the solvent (D), if it is within the above range, is a spin coater, a slit and a spin coater, and a slit coater (also referred to as a die coater or a curtain coater). In the case of a cloth machine, it is preferable that the coating device such as an ink jet has a coating property at the time of coating.

In the photosensitive resin composition of the present invention, a filler, another polymer compound, a pigment dispersant, an adhesion promoter, an oxidation inhibitor, an ultraviolet absorber, a coagulation preventing material, a chain transfer agent, or the like may be used in combination as necessary. Additive (F).

Examples of the filler include glass, cerium oxide, aluminum oxide, pigment, and the like.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleic imine resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. , thermoplastic resins such as polyester and polyurethane, and the like.

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include a surfactant such as an anthracene-based, a fluorine-based, an ester-based, a cationic, an anionic, a nonionic or an amphoteric, each of which is used alone or in combination. Above Can be used. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modified polyesters. In addition to the grade 3 amine-denatured polyurethanes and polyethyleneimine, there are also trade names KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoei Chemical Co., Ltd.), and FTOP (Donghua Products Co., Ltd.). System, MEGAFACE (made by Dainippon Ink Chemical Industry Co., Ltd.), Fluorad (manufactured by Sumitomo 3M Co., Ltd.), AsahiGuard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Syngenta Co., Ltd.), EFKA (made by EFKA CHEMICALS), PB821 (made by Ajinomoto Co., Ltd.), etc.

Examples of the adhesion promoter include ethylene trimethoxy decane, ethylene triethoxy decane, ethylene tris(2-methoxyethoxy) decane, and N-(2-aminoethyl)-3-. Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidol Ether oxypropyltrimethoxydecane, 3-glycidyloxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyl Trimethoxy decane, 3-chloropropyltrimethoxydecane, 3-methacryloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like.

Examples of the oxidation preventive agent include 2,2'-thiobis(4,methyl-6-tert-butylphenol) and 2,6-di-t-butyl-4-cresol.

Examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

Moreover, as for the aggregation inhibitor, sodium polyacrylate etc. are mentioned, for example.

Examples of the chain transfer agent include, for example, dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

The photosensitive resin composition can be applied to a substrate, for example, by photohardening and development to form a pattern. First, the composition is applied on a substrate (usually glass) or a layer of a solid material of a preformed photosensitive resin composition, or ITO (indium-tin oxide) or IZO (indium) is formed. On the substrate of the zinc oxide), a smooth coating film is obtained by pre-baking the volatile component such as a solvent from the applied photosensitive resin composition layer. The film thickness at this time is usually about 1 to 6 μm. The coating film obtained in such a manner is irradiated with ultraviolet rays through a photomask for forming a target pattern. At this time, it is preferable to illuminate the parallel light rays entirely and uniformly with the exposed portion, and the correct position of the photomask and the substrate is aligned, and a device such as a mask aligner or a stepper is preferably used. Further, after that, the coating film which has been subjected to the hardening is brought into contact with the alkaline aqueous solution to dissolve the non-exposed portion, and the desired pattern shape can be obtained. The development method may be any of a liquid pool method, a dipping method, a spray method, and the like. In addition, it is also possible to tilt the substrate at an arbitrary angle during development.

The developing solution used for development after patterning and exposure is usually an aqueous solution containing a basic compound and a surfactant.

The basic compound is either an inorganic or an organic basic compound. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, and phosphoric acid. Ammonium hydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like.

Further, specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, and Ethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic basic compounds may be used alone or in combination of two or more. The concentration of the basic compound in the alkali developing solution is preferably from 0.01 to 10% by mass, preferably from 0.03 to 5% by mass.

The surfactant in the alkali developing solution may be any of a nonionic surfactant, an anionic surfactant or a cationic surfactant.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aromatic ether, polyoxyethylene alkyl aromatic ether, other polyoxyethylene derivatives, and oxyethylene/oxypropylene block copolymerization. , sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine Wait.

Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate or sodium oleyl sulfate, alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate, and twelve An alkyl aromatic sulfonate such as sodium benzenesulfonate or sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include an amine salt such as stearylamine hydrochloride or lauric trimethylammonium chloride or a fourth-order ammonium salt.

These surfactants may be used singly or in combination of two or more kinds.

The concentration of the surfactant in the alkali developing solution is preferably in the range of 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.

After the development, the water is washed, and further, if necessary, may be baked at 150 to 230 ° C for 10 to 60 minutes.

Using the photosensitive resin composition of the present invention, a pattern can be formed on the substrate or on the filter substrate by the respective processes as described above. This pattern is useful as a photo spacer used in a liquid crystal display device. Further, when the dried coating film is subjected to pattern forming exposure, a hole can be formed by using a mask for forming a hole, and it is useful as an interlayer insulating film. The pattern arrangement of the reticle can be arbitrarily changed in shape, size, and pitch. Further, when the dried coating film is exposed, it is possible to form a transparent film by performing full exposure and heat curing without using a photomask, or to form a transparent film by heat curing only. This transparent film is useful as a protective film, and can also be used for Touch panel.

By forming the pattern thus obtained and forming it in a display device such as a liquid crystal display device, it is possible to manufacture an excellent crystal display device with high yield.

In the photosensitive resin composition of the present invention, even on a transparent conductive film such as ITO (indium-tin oxide), a pattern having a fine line width can be formed without falling off, and the pattern is excellent in solvent resistance and heat resistance.

The photosensitive resin composition of the present invention can be suitably used for forming a transparent film constituting a part of a filter, such as a protective film, a photo spacer, an insulating film, a liquid crystal alignment control protrusion, and an alignment coloring pattern. Film thickness A transparent film such as a coating layer or the like can be suitably used for a filter or a display device including the same.

Example

In the following, the invention will be explained in more detail in accordance with the embodiments, but it is obvious that the invention is not limited by the embodiments. In the examples, the % or the part indicating the content or the amount used is a quality standard unless otherwise specified.

Synthesis Example 1

A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was passed through a nitrogen atmosphere at 0.02 L/min, and 200 parts by mass of 3-methoxy-1-butanol and 3-methoxybutyl acetate were added. 105 parts by mass, heated to 70 ° C while stirring. Next, 55 parts by mass of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1), 70 parts by mass of a molar ratio of 50:50.) 70 parts by mass of N-cyclohexylmaleimine, dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was prepared. It took 4 hours to use a drip pump and was dropped into a flask maintained at 70 °C. On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in a solution of 225 parts by mass of 3-methoxybutyl acetate, and another solution is used. A drip pump took 5 hours to drip into the flask. After the solution of the polymerization initiator was finished, it was kept at 70 ° C for 4 hours, and then cooled to room temperature with a viscosity (23 ° C) of 114 mPa. s, a solid matter of 32.6% by mass, gave a solution of a copolymer (resin AA) having an acid value of 34.3 mg-KOH/g. The obtained resin AA had a weight average molecular weight Mw of 13,600 and a degree of dispersion of 2.54.

In addition, the viscosity of the copolymer solution was measured by a Brookfield viscometer.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the above-mentioned binder polymer was carried out under the following conditions using a GPC method.

Device: K2479 (made by Shimadzu Corporation) Column: SHIMADZU Shim-pack GPC-80M Column temperature: 40 ° C Solvent: THF (tetrahydrofuran) Flow rate: 1.0mL/min Detector: RI

The ratio of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained in the above manner is defined as the degree of dispersion (Mw/Mn).

Example 1

<Preparation of photosensitive resin composition> In the resin solution portion (55 parts in terms of solid content) of the resin AA obtained in Synthesis Example 1, 40 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) was mixed, and caprolactone denatured polyfunctional 5 parts of acrylate (KAYARAD DPCA-120, manufactured by Nippon Kayaku Co., Ltd.), 6 parts of 2-methyl-2-morpholinyl (4-thiomethylphenyl) propan-1-one, propylene glycol monomethyl 53 parts of ether acetate, 20 parts of 3-ethoxyethyl propionate, 37 parts of 3-methoxy 1-butanol and 87 parts of 3-methoxybutyl acetate Thus, a photosensitive resin composition 1 was obtained.

<Formation of Pattern> A substrate of an ITO film (having a film thickness of 1500 A and a resistance of 10 Ω/sq) was formed on a 2 inch square glass substrate (#1737; manufactured by Corning Incorporated), and washed sequentially with a neutral detergent, water, and alcohol. Dry after the net. On the glass substrate, the photosensitive resin composition 1 was exposed to an exposure amount (365 nm) of 100 mJ/cm ² , and the film thickness after the respective processes of development, water washing, and post-baking was 3.5 μm. Coating, followed by hot plate, pre-baked at 75 ° C for 2 minutes. After cooling, the distance between the substrate on which the photosensitive resin composition was applied and the mask made of quartz glass was set to 10 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used, and the atmosphere atmosphere was 100 mJ/cm. The exposure amount of ² (365 nm reference) was irradiated with light.

Further, as the photomask, a photomask formed on the same plane with the following pattern was used.

‧ With 5,600 light-transmissive portions (patterns) of 7 μm on each side, the squares are 100 μm apart.

After the light irradiation, the coating film was immersed at 23 ° C for 80 seconds in a water-based developing solution containing 0.12% of a nonionic surfactant and 0.05% of potassium hydroxide, and was subjected to ultrasonic cleaning (frequency 38 kHz) for 20 After washing in a minute, it was baked in an oven at 230 ° C for 20 minutes. After cooling, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Save stability> The viscosity of the photosensitive resin composition 1 obtained above was measured. Then, the photosensitive resin composition 1 was sealed in a light-shielding container which was stored in a thermostat at 23 ° C for 2 weeks.

The viscosity of the photosensitive resin composition 1 after storage was measured. The viscosity change obtained according to the following formula is 100%.

The smaller the viscosity change, for example, as long as it is in the range of 100 to 103%, the better. In addition, the measurement of the viscosity was carried out as follows.

In addition, the viscosity was measured at 23 ° C using a viscometer (VISCOMETER TV-30; manufactured by Toki Sangyo Co., Ltd.).

<transmittance> In the exposure process of the pattern formation described above, the film thickness is 2.9 to 3.1 μm except that the mask is not used, and the same operation as described above is performed to form a cured film, and the film thickness is measured for the film thickness. A device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) was used for the measurement.

Then, the transmittance (%) at 400 nm of the obtained cured film was measured using a microspectrophotometer (OSP-SP200; manufactured by OLYMPUS Co., Ltd.), and the transmittance was converted to a transmittance of 3.0 μm in film thickness. , for 96.3%.

<surface smoothness> A cured film was produced in the same manner as described above except that the photosensitive resin composition 1 was used and the photomask was not used. The obtained cured film was evaluated for the items shown in Table 2.

The surface of the obtained cured film was observed using a scanning electron microscope (S-4000; manufactured by Hitachi, Ltd.).

The case where the surface of the cured film was smooth was set to ○, and the case where the unevenness was formed was evaluated as ×.

<pattern shape> The line width of the pattern used for the measurement of the surface smoothness was 7.9 μm when measured by a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.).

The shape is observed from the front side of the pattern. The case where the width of the lower bottom line is larger than the upper bottom is classified as a straight cone, and the case where the widths of the upper bottom and the lower bottom are equal is classified as a rectangle, and the width of the lower bottom line is classified as a reverse cone when the width of the lower bottom is smaller than the upper base.

When the pattern shape is a rectangle, the development adhesion tends to be good, and it is preferable.

<Dynamic adhesion> In the above-mentioned pattern forming process, the substrate after the image is immersed in a 1 L glass beaker containing 500 mL of pure water, and the ultrasonic cleaning machine (US-4, measuring frequency; 38 kHz, SND) is carried out at 23 to 25 ° C. Company limited After 10 minutes and 20 minutes of water washing, the number of pattern peelings in 5600 was calculated. The number of peelings is 0, and there is no peeling at all. The less the number of peeling, the better the image can be said to be better.

<Mechanical characteristics (total displacement amount and recovery rate)> For a hardened pattern obtained by forming the pattern described above, a dynamic ultra-micro hardness tester (DUH-W201; manufactured by Shimadzu Corporation) was used to measure the total amount of displacement (μm) and the amount of elastic displacement (μm). And calculate the response rate (%).

- Measurement conditions - Test mode; load-load test Test force; 20mN Load speed; 4.4mN/sec Hold time; 5sec Compressor; cone-shaped pressure (diameter 50μm)

Recovery rate (%); [elastic displacement (μm) / total displacement (μm)] × 100

In the mechanical properties, when the film thickness is 3 to 5 μm and the line width is 7 to 10 μm, the total displacement amount is 0.90 μm or more, and the pattern having a recovery ratio of 45% or more can be said to be good.

<Solvent resistance> In the exposure process of the aforementioned pattern formation, except that no photomask is used. The same operation was carried out to prepare a coating film, and the film thickness and transmittance were measured. The produced coating film was immersed in N-methylpyrrolidone at 30 ° C for 30 minutes, and the film thickness and transmittance after immersion were measured, and the change was obtained according to the following formula.

Film thickness change (%); [film thickness after immersion (μm) / film thickness before immersion (μm)] × 100 Transmittance change (%); [transmittance after immersion (%) / transmittance before immersion (%)] × 100

The film thickness change and the transmittance change are preferably 90 to 103%, respectively.

Solvent resistance; On the coated film after the immersion test of the heat resistance test, 100 squares each having a side of 1 mm were produced using a commercially available utility knife. The peel test was carried out using a commercially available celluloid tape, and the following values were used for evaluation.

[(Number of squares remaining on the substrate without peeling off) / 100] The larger value is excellent in adhesion and can be said to be good.

<heat resistance> In the exposure process of the pattern formation described above, the same operation was carried out except that the photomask was not used, and a coating film was produced. The prepared coating film was allowed to stand in a clean oven at 240 ° C for 1 hour, and the film thickness and transmittance (measuring wavelength; 400 nm) before and after heating were measured, and the changes were obtained according to the following formula. As a result, the film thickness change was 92.4%. Also, the transmittance change was 96.3%.

Film thickness change (%); [film thickness after heating (μm) / film thickness before heating (μm)] × 100 Transmittance change (%); [transmittance after heating (%) / transmittance before heating (%)] × 100

The change in film thickness and the change in transmittance were good in the case of 90 to 103%, respectively.

Heat-resistance; 100 squares of 1 mm on each side were produced using a commercially available utility knife on the heated film after the heat resistance test. The peel test was carried out using a commercially available celluloid tape, and the following values were used for evaluation.

[(the number of squares remaining on the substrate without being peeled off) / 100] The value is excellent, and the adhesion is excellent.

Example 2

In the same manner as in Example 1, the photosensitive resin composition 2 was obtained in the same manner as in Example 1 and evaluated. Represent the result In Table 2.

Example 3

In the same manner as in Example 1, the photosensitive resin composition 3 was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

Comparative example 1

In the same manner as in Example 1, the photosensitive resin composition 4 was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

As a result of the examples 1 to 3 shown in Table 2, when the photosensitive resin composition of the present invention is used, even when a fine pattern is formed, a pattern excellent in image formation can be formed, and thus the process range is obtained. It is wide. Further, it is understood that the pattern formed and the coating film having excellent pattern shape, surface smoothness, mechanical properties, heat resistance, and solvent resistance can be obtained.

On the other hand, the photosensitive resin composition of Comparative Example 1 which does not contain a compound having an unsaturated double bond bonding equivalent of from 120 to 400 g/eq can only obtain a developer with poor adhesion.

Industrial use possibility

The photosensitive resin composition of the present invention is a pattern and a coating film which are excellent in stability and can form a pattern shape, surface smoothness, mechanical properties, heat resistance, and solvent resistance, and can be suitably used for a protective film or light. The formation of a transparent film used for a display device such as a spacer, an insulating film, a projection for liquid crystal alignment control, and a coating layer for aligning a film thickness of a colored pattern.

Claims (5)

A photosensitive resin composition containing a photosensitive resin composition of a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D), the binder resin ( A) is an unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (A1), and an aliphatic polycyclic epoxy compound (A2), and is different from (A1) and (A2) and can be combined with (A1) and A2) a copolymer of the monomer (A3) copolymerized, and the photopolymerizable compound (B) contains a compound having an unsaturated double bond binding equivalent of from 120 to 400 g/eq. The photosensitive resin composition of claim 1, wherein the compound having an unsaturated double bond binding equivalent of from 120 to 400 g/eq is a compound represented by the formula (BA). [In the formula (BA), R ^a to R ^f each independently represent a hydrogen atom or a group represented by the formula (BA-1) to (BA-3), At least four of R ^a to R ^{f are} represented by any one of formulas (BA-1) to (BA-3), and at least one of R ^a to R ^{f is} of formula (BA-2) or (BA-3) indicates the basis]. The photosensitive resin composition according to claim 1 or 2, wherein the aliphatic polycyclic epoxy group-containing monomer (A2) is selected from the group consisting of the compound represented by the formula (I) (II) at least one compound of the group consisting of the compounds, [In the formulae (I) and (II), R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group, and X each independently represents a single bond or a hetero atom. The alkyl group has a carbon number of 1 to 6]. A pattern formed by using a photosensitive resin composition as set forth in claims 1 to 3 of the patent application. A display device comprising a pattern as in item 4 of the patent application.