CN101261447A - Phototonus resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition comprising a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D). The binder resin (A) are unsaturated carboxylic acids and/or unsaturated carboxylic acid anhydrides (A1), aliphatic polycyclic epoxy compounds (A2) and monomers other than (A1) and (A2) that can be copolymerized with (A1) and (A2) (A3), and the photopolymerizable compound (B) contains a compound having an unsaturated double bond equivalent of 120 to 400 g/eq. Using this photosensitive resin composition, a fine line width pattern can also be formed on a transparent conductive film such as ITO (indium-tin oxide).

Description

Photosensitive resin composition

technical field

The present invention relates to a photosensitive resin composition.

Background technique

In a liquid crystal display device, a touch panel, and the like, a spacer is provided between a color filter constituting the display device and an array substrate in order to maintain a distance between the two substrates. At present, spherical particles such as glass beads and plastic beads are used as the spacers.

However, if such spherical particles are used, since the spherical particles are scattered randomly on the glass substrate, damage to the TFT element and electrodes, etc. will be caused. The scattering of the liquid crystal display element will decrease the contrast. Therefore, a method of forming spacers from a photosensitive resin composition instead of spherical particles has been proposed. When this method is applied, since the spacer can be formed at an arbitrary location, the above-mentioned problems can be solved.

As such a photosensitive resin composition, it is known to contain an acrylic copolymer having a carboxyl group and a glycidyl ether group as a binder resin, and dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.) as a photopolymerizable compound. ) produced KAYARAD DPHA, unsaturated double bond equivalent: 105g/eq) composition (refer to Patent Document 1), and disclosed that when spacer patterns are formed using this composition, excellent solvent resistance and heat resistance can be obtained Spacer pattern.

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

However, when using this photosensitive resin composition to form a spacer pattern on a transparent conductive film such as ITO (indium-tin oxide), if it is a fine pattern, the surface smoothness will be caused by the pattern coming off during the development and washing steps. drop problem.

Contents of the invention

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

The inventors of the present invention have studied a photosensitive resin composition capable of solving the above-mentioned problems, and found that when the photosensitive resin composition contains a photopolymerizable compound having an unsaturated double bond equivalent within a certain range, fine line width can be formed. picture of.

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

[1]. A photosensitive resin composition comprising 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 an unsaturated carboxylic acid anhydride (A1), an aliphatic polycyclic epoxy compound (A2) and a compound different from (A1) and (A2) that can be copolymerized with (A1) and (A2) A copolymer of a monomer (A3), and a photopolymerizable compound (B) containing a compound having an unsaturated double bond equivalent of 120 to 400 g/eq.

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

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

At least four bases in R ^a -R ^f are any base shown in formula (BA-1)～(BA-3), at least one base in R ^a -R ^f is formula (BA-2) or formula ( The group shown in BA-3). ]

[3]. The photosensitive resin composition as described in [1] or [2], wherein the monomer (A2) having an aliphatic polycyclic epoxy group is selected from compounds represented by formula (I) and formula ( At least one compound among the compounds represented by II).

[In formula (I) and formula (II), R independently represents hydrogen atom or the alkyl group of carbon atom number 1-4 that can be substituted by hydroxyl,

X each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may contain a heteroatom. ]

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

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

Detailed ways

Next, 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), the photopolymerization initiator (C), and optional other additives (F) are dissolved or dispersed in the solvent (D) middle. The photosensitive resin composition of the present invention is preferably used mainly as a pattern forming material.

The binder resin (A) used in the present invention is an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride (A1), an aliphatic polycyclic epoxy compound (A2), and other than (A1) and (A2) but Copolymers of monomers (A3) which can be copolymerized with (A1) and (A2). The binder resin (A) preferably has alkali solubility.

As the above-mentioned unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride (A1), specifically, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid can be cited;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid (methyl fumaric acid), itaconic acid and other unsaturated dicarboxylic acids;

and the above-mentioned unsaturated dicarboxylic acid anhydrides;

Unsaturated mono[ (meth)acryloyloxyalkyl] esters;

Unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid, and the like.

Among them, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferably used in view of copolymerization reactivity and solubility in an alkaline aqueous solution. These can be used individually or in combination of 2 or more types.

The above-mentioned aliphatic polycyclic epoxy compound (A2) is a compound having an epoxy group on the ring of the aliphatic polycyclic compound, and the above-mentioned aliphatic polycyclic epoxy compound (A2) is preferably in the aliphatic polycyclic epoxy compound. A polycyclic compound is a compound that has an epoxy group in the ring and an unsaturated bond. As this aliphatic polycyclic compound, dicyclopentane, tricyclodecane, etc. are mentioned, for example.

As an aliphatic polycyclic epoxy compound (A2), at least 1 sort(s) of compound chosen from the compound represented by (I) and the compound represented by formula (II) is mentioned preferably.

In formula (I) and formula (II), R independently represents a hydrogen atom or an alkyl group with 1-4 carbon atoms that may be substituted by a hydroxyl group,

X each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may contain a heteroatom.

As R, specifically, a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and other alkyl groups; hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxy-isopropyl, 2-hydroxy-isopropyl, 1-hydroxy- Hydroxyl-containing alkyl groups such as n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, and 4-hydroxy-n-butyl. Among these, hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are preferable, and hydrogen atom and methyl group are more preferable.

Specific examples of X include single bonds; alkylene groups such as methylene, ethylene, and propylene; oxymethylene, oxyethylene, oxypropylene, and thiomethylene. , thioethylene, thiopropylene, aminomethylene, aminoethylene, aminopropylene, and other heteroatom-containing alkylene groups. Among these, a single bond, a methylene group, an ethylene group, an oxymethylene group, and an oxyethylene group are preferably used, and a single bond and an oxyethylene group are more preferably used.

As the compound represented by formula (I), for example, compounds represented by formula (I-1) to formula (I-15) etc., preferably enumerated formula (I-1), formula (I-3), formula (I- 5), formula (I-7), formula (I-9), formula (I-11) ~ formula (I-15), more preferably enumerate formula (I-1), formula (I-7), formula ( I-9), formula (I-15).

As a compound represented by formula (II), for example, compounds represented by formula (II-1) to formula (II-15) can be cited, and formula (II-1), formula (II-3), formula (II- 5), formula (II-7), formula (II-9), formula (II-11) ~ formula (II-15), more preferably enumerate formula (II-1), formula (II-7), formula ( II-9), formula (II-15).

At least one compound selected from the compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination at any ratio. When mixing, the mixing ratio is in molar ratio, preferably formula (I): formula (II) is 5:95～95:5, more preferably 10:90～90:10, more preferably 20:80～80: 20.

As the above-mentioned monomer (A3) which is different from (A1) and (A2) but can be copolymerized with (A1) and (A2), for example, methyl (meth)acrylate, ethyl (meth)acrylate, ( Alkyl (meth)acrylates such as n-butyl methacrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, etc. Alkyl acrylates such as methyl acrylate and isopropyl acrylate (Meth) acrylate cyclohexyl ester, (meth) acrylate 2-methylcyclohexyl ester, (meth) acrylate tricyclo [5.2.1.0 ^2,6 ] decane-8 base ester (in this technical field , as its common name, called (meth)acrylate dicyclopentyl), (meth)acrylate dicyclopentyloxyethyl ester, (meth)acrylate isobornyl (isoboronil) etc. (meth) Cyclic alkyl acrylates; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[ ^5.2.1.02,6 ]decane-8yl acrylate (in this technical field, as its common name , known as dicyclopentyl acrylate), dicyclopentyloxyethyl acrylate, isobornyl acrylate and other cyclic alkyl acrylates; phenyl (meth)acrylate, benzyl (meth)acrylate Aryl (meth)acrylates such as esters; aryl acrylates such as phenyl acrylate and benzyl acrylate; diethyl maleate, diethyl fumarate, diethyl itaconate dicarboxylic acid diesters such as esters; hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 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-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] Hept-2-ene, 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-ethyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]heptene -2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5 -Carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (norbornene dicarboxylic anhydride), 5- tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1 ]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1 ]hept-2-ene and other bicyclic unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-Succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-succinimidyl-3-maleimide Iminopropionate, N-(9-acridyl)maleimide and other dicarbonylimide derivatives;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, propylene Amide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate Esters, α-glycidyl ethacrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4 methacrylate - Epoxybutyl, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethacrylate, ortho - Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like.

Among these substances, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-benzyl Maleimide, bicyclo[2.2.1]hept-2-ene, etc. These substances may be used alone or in combination of two or more.

The binder resin (A) used in the present invention is a polymer obtained by copolymerizing (A1), (A2) and (A3), and the ratio of the constituents derived from them is expressed relative to the constituents constituting the copolymer The mole percentage of the total number of moles is preferably in the following range.

Structural units derived from (A1): 2 to 40 mol%

Structural units derived from (A2): 2 to 95 mol%

Structural units derived from (A3): 1 to 65 mol%

In addition, it is more preferable that the ratio of the above-mentioned constituent components is within the following range.

Structural units derived from (A1): 5-35 mol%

Structural unit derived from (A2): 5-80 mol%

Structural units derived from (A3): 1 to 60 mol%

When the said composition ratio is in the said range, the storage stability of a photosensitive resin composition, the developability of the pattern obtained from this composition, solvent resistance, heat resistance, and mechanical strength tend to become favorable.

The above-mentioned binder resin (A) can be referred to, for example, the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Doujin 1st Edition, 1st Printing, March 1, 1972 issue) and this References cited in the literature were prepared.

Specifically, a prescribed amount of each compound for obtaining each structural unit (A1), (A2) and (A3) of the copolymer, a polymerization initiator, and a solvent is added to a reaction vessel, and oxygen is replaced with nitrogen, thereby in the absence of oxygen A polymer can be obtained by stirring, heating, and retaining heat in the presence of the polymer. In addition, the obtained copolymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like.

The polystyrene conversion weight average molecular weight of the said binder resin (A) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. If the weight-average molecular weight of the binder resin (A) is within the above range, the applicability tends to be improved, film shrinkage is less likely to occur during development, and the detachability of non-pixel parts during development is good, so it is preferred.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the binder resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the molecular weight distribution is within the above range, it tends to be excellent in developability, which is preferable.

The content of the binder resin (A) used in the photosensitive resin composition of the present invention is relative to the solid content in the photosensitive resin composition (among the components of the composition, it refers to a substance that is solid at 25° C.) by In weight percentage, it is preferably 5 to 90% by weight, more preferably 10 to 70% by weight. If the content of the binder resin (A) is within the above range, the solubility to the developer is sufficient, and the development residue is not easily generated on the substrate of the non-pixel part, and in addition, film shrinkage of the pixel part of the exposed part is not easy to occur during development, Since the detachability of the non-pixel portion tends to be improved, it is preferable.

The photopolymerizable compound (B) used for this invention contains the compound whose unsaturated double bond equivalent is 120-400 g/eq. As the compound having an unsaturated double bond equivalent weight of 120 to 400 g/eq, a compound represented by the formula (BA) is preferably used.

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

At least four bases in R ^a -R ^f are any base represented by formula (BA-1)～(BA-3), at least one base in R ^a -R ^f is formula (BA-2) or formula (BA -3) The base represented.

As the compound represented by formula (BA), among R ^a -R ^f , two are hydrogen atoms, three are groups represented by formula (BA-1), and one is a compound represented by formula (BA-2). Two are hydrogen atoms, three are the base represented by formula (BA-1), and one is the compound of the base represented by formula (BA-3); two are hydrogen atoms, two are represented by formula (BA-1) two groups represented by formula (BA-2); two hydrogen atoms, two groups represented by formula (BA-1), one group represented by formula (BA-2), one It is the compound of the base represented by formula (BA-3); two are hydrogen atoms, two are the bases represented by formula (BA-1), and two are the compounds of the base represented by formula (BA-3); two are Hydrogen atom, one is a group represented by formula (BA-1), three are compounds of groups represented by formula (BA-2); two are hydrogen atoms, one is a group represented by formula (BA-1), two It is a group represented by formula (BA-2), and one is a compound represented by formula (BA-3); two are hydrogen atoms, one is a group represented by formula (BA-1), and one is a group represented by formula (BA-2 ), two are compounds represented by formula (BA-3); two are hydrogen atoms, one is a group represented by formula (BA-1), and three are groups represented by formula (BA-3) two are hydrogen atoms, four are compounds represented by formula (BA-2); two are hydrogen atoms, three are groups represented by formula (BA-2), and one is the group represented by formula (BA-3 ) represented by the compound; two hydrogen atoms, two groups represented by the formula (BA-2), two compounds represented by the formula (BA-3); two hydrogen atoms, one represented by the formula The base represented by (BA-2), three compounds of the base represented by the formula (BA-3); two are hydrogen atoms, four are compounds of the base represented by the formula (BA-3); one is a hydrogen atom, Four are the bases represented by formula (BA-1), one is the compound of the base represented by formula (BA-2); one is a hydrogen atom, four are bases represented by formula (BA-1), and one is the base represented by formula (BA-2). -3) the compound of the base represented; one is a hydrogen atom, three are the bases represented by the formula (BA-1), and two are the compounds of the base represented by the formula (BA-2); one is a hydrogen atom, three are A group represented by formula (BA-1), one is a group represented by formula (BA-2), and one is a compound represented by a group represented by formula (BA-3); one is a hydrogen atom, and three are compounds of formula (BA-1) The group represented by two is the compound of the group represented by the formula (BA-3); one is a hydrogen atom, two are the groups represented by the formula (BA-1), and three are the groups represented by the formula (BA-2) Compound; one is a hydrogen atom, two are the bases represented by formula (BA-1), two are the bases represented by formula (BA-2), and one is the compound of the base represented by formula (BA-3); one is hydrogen Atoms, two groups represented by formula (BA-1), one group represented by formula (BA-2), and two groups represented by formula (BA-3); one is a hydrogen atom, two are The base represented by formula (BA-1), three compounds of the base represented by formula (BA-3); one is a hydrogen atom, one is the base represented by formula (BA-1), and four are compounds represented by formula (BA-2 ) represented by a compound; one is a hydrogen atom, one is a group represented by formula (BA-1), three are represented by formula (BA-2), and one is a compound represented by formula (BA-3) ; One is a hydrogen atom, one is a base represented by formula (BA-1), two are bases represented by formula (BA-2), and two are compounds of bases represented by formula (BA-3); one is a hydrogen atom , one is a base represented by formula (BA-1), one is a base represented by formula (BA-2), and three are compounds of groups represented by formula (BA-3); one is a hydrogen atom, and one is a compound of formula (BA -1) the group represented, four are the compound of the group represented by the formula (BA-3); one is a hydrogen atom, five are the compounds of the group represented by the formula (BA-2); one is a hydrogen atom, four are The base represented by formula (BA-2), one is the compound of the base represented by formula (BA-3); one is a hydrogen atom, three are the bases represented by formula (BA-2), two are the bases represented by formula (BA-3 ) represented by the compound; one is a hydrogen atom, two are the group represented by the formula (BA-2), and three are the compounds represented by the formula (BA-3); one is a hydrogen atom, and one is the compound of the formula (BA-2) -2) the base represented, four are the compounds of the base represented by the formula (BA-3); one is a hydrogen atom, five are the compounds of the base represented by the formula (BA-3); five are the compounds of the base represented by the formula (BA-1 ), one is a compound represented by formula (BA-2); five are compounds represented by formula (BA-1), one is a compound represented by formula (BA-3); four are compounds represented by formula The base represented by (BA-1), two are the compounds of the base represented by the formula (BA-2); four are the base represented by the formula (BA-1), one is the base represented by the formula (BA-2), one It is the compound of the group represented by formula (BA-3); four are the group represented by formula (BA-1), two are the compounds of the group represented by formula (BA-3); three are the group represented by formula (BA-1) The group represented, three are the compound of the group represented by formula (BA-2); three are the group represented by formula (BA-1), two are the group represented by formula (BA-2), one is the group represented by formula (BA -3) the compound of the group represented; three are the group represented by the formula (BA-1), one is the group represented by the formula (BA-2), and two are the compounds represented by the group represented by the formula (BA-3); three One is a group represented by formula (BA-1), three are compounds represented by formula (BA-3); two are groups represented by formula (BA-1), and four are represented by formula (BA-2) The compound of the base; two are the bases represented by the formula (BA-1), three are the bases represented by the formula (BA-2), and one is the compound of the base represented by the formula (BA-3); two are the bases represented by the formula ( BA-1), two groups represented by formula (BA-2), two compounds represented by formula (BA-3); two groups represented by formula (BA-1), one It is a group represented by formula (BA-2), three are compounds represented by formula (BA-3); two are groups represented by formula (BA-1), and four are represented by formula (BA-3) One is a compound represented by formula (BA-1), five are compounds represented by formula (BA-2); one is a group represented by formula (BA-1), and four are represented by formula (BA- 2) the group represented, one is the compound of the group represented by the formula (BA-3); one is the group represented by the formula (BA-1), three are the groups represented by the formula (BA-2), two are the group represented by the formula ( BA-3) is a compound represented by the group; one is the group represented by the formula (BA-1), two are the group represented by the formula (BA-2), and three are the compounds represented by the group represented by the formula (BA-3); One is a group represented by formula (BA-1), one is a group represented by formula (BA-2), and four are compounds represented by a group represented by formula (BA-3); one is a group represented by formula (BA-1) , five are compounds of groups represented by formula (BA-3); six are compounds of groups represented by formula (BA-2); five are groups represented by formula (BA-2), and one is group represented by formula (BA- 3) The compound of the base represented; Four are the base represented by formula (BA-2), two are the compounds of the base represented by formula (BA-3); three are the base represented by formula (BA-2), three One is the compound of the group represented by formula (BA-3); two are the group represented by formula (BA-2), and four are compounds of the group represented by formula (BA-3); one is the compound of group represented by formula (BA-2) The group represented, five compounds represented by the group represented by the formula (BA-3); six compounds represented by the group represented by the formula (BA-3), etc.

Among them, it is more preferable to enumerate the compound whose unsaturated double bond equivalent is 200-350g/eq, as the compound, can enumerate the compound whose six groups are represented by formula (BA-2); ) The compound represented by the group.

Examples of the compound represented by formula (BA) include KAYARAD DPCA-20 in which two are compounds represented by formula (BA-2) and three compounds represented by formula (BA-2) among R ^a to R ^f KAYARAD DPCA-30, six KAYARAD DPCA-60 of the compound represented by the formula (BA-2), six KAYARAD DPCA-120 of the compound represented by the formula (BA-3) (all manufactured by Nippon Kayaku Co., Ltd.) and other commercially available substances.

Examples of the photopolymerizable compound contained in the photopolymerizable compound (B) other than the compound represented by the formula (BA) include trifunctional or higher polyfunctional monomers.

Specific examples of polyfunctional monomers having three or more functions include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, penta(meth)acrylate, ) dipentaerythritol acrylate, dipentaerythritol hexa(meth)acrylate, reactants of pentaerythritol tri(meth)acrylate and acid anhydride, reactants of dipentaerythritol penta(meth)acrylate and acid anhydride, etc. Among these, it is preferable to use a tetrafunctional or more polyfunctional monomer. These photopolymerizable compounds may be used alone or in combination of two or more.

The content of the photopolymerizable compound (B) is preferably 1 to 70% by weight, more preferably 5 to 60% by weight, based on the total amount of the binder resin (A) and the photopolymerizable compound (B), in percentage by weight. . When the content of the photopolymerizable compound (B) is within the above range, the intensity, smoothness, and reliability of the pixel portion tend to be improved, which is preferable.

In addition, the content of the compound represented by the formula (BA) is usually 3 to 100 wt. %, preferably 3 to 70% by weight, more preferably 3 to 50% by weight, even more preferably 5 to 40% by weight. When the content of the compound represented by the formula (BA) is within the above range, the balance between the sensitivity and the image development adhesiveness tends to be better, so it is preferable.

As a photoinitiator (C) contained in the photosensitive resin composition of this invention, acetophenone type, bidiimidazole type, oxime type, triazine type, acylphosphine oxide type initiator are mentioned, for example. By using these photopolymerization initiators (C) in combination with the photopolymerization initiation auxiliary agent (C-1), the photosensitive resin composition obtained can be made to have higher photosensitivity, so if the photopolymerization initiation auxiliary agent (C-1) is used in combination C-1) Forming a pattern is preferable since the productivity of the pattern can be improved.

Examples of the aforementioned acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 2-hydroxy -1-[4-(2-Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthio Substituted phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(2 -Methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-( 4-morpholinophenyl)-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2- Ethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4 -morpholinophenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2,3 -Dimethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-dimethylamino -1-(4-morpholinophenyl)-butanone, 2-(2-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2 -(2-Bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino- 1-(4-morpholinophenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2- (3-Bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1 -(4-morpholinophenyl)-butanone, 2-(2-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2- (3-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino -1-(4-morpholinophenyl)-butanone, 2-(2-methyl-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl )-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromobenzyl) -4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-hydroxy-2-methyl-1-[4-(1-methyl Oligomers of vinyl)phenyl]propan-1-one, etc.

Examples of the above-mentioned biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4'-5,5'-tetraphenylbiimidazole, 2,2'-bis(2 , 3-dichlorophenyl)-4,4',5,5'-tetraphenylbidiimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.), 2,2 '-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5 , 5'-tetrakis(alkoxyphenyl) bis-diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl) Bidiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bidiimidazole (for example, see Patent Publication No. 48-38403 Publication, JP-A-62-174204, etc.), 4,4', 5,5'-position phenyl is substituted by an alkoxycarbonyl imidazole compound (for example, refer to JP-A-7-10913, etc.), preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-Tetraphenylbidiimidazole.

Examples of the oxime compound include O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, compounds represented by formula (3), compounds represented by formula (4), and the like.

As above-mentioned triazine compounds, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis( Trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-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)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2- Base) 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-tri Zinc, etc.

Examples of the above-mentioned acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Moreover, as long as the effect of this invention is not impaired, you may further use together the photoinitiator etc. which are commonly used in this field. Examples of the photopolymerization initiator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds.

More specific examples include the following compounds, which can be used alone or in combination of two or more.

As said benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether etc. are mentioned, for example.

Examples of the above-mentioned benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl Sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Examples of the above-mentioned thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Ketones, 1-chloro-4-propoxythioxanthone, etc.

Examples of the above-mentioned anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene and so on.

In addition, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzil, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound etc. as photopolymerization initiators.

In addition, as the photopolymerization initiator having a group causing chain transfer, a photopolymerization initiator described in Japanese Patent Application Publication No. 2002-544205 can also be used.

As a photoinitiator which has the said group which causes a chain transfer, the photoinitiator of formula (5)-(10) is mentioned, for example.

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

Moreover, a photopolymerization start adjuvant (C-1) can also be used together with a photoinitiator. As the photopolymerization start aid, it is preferable to use an amine compound and a carboxylic acid compound, and it is preferable to use an aromatic amine compound as the amine compound.

Specific examples of photopolymerization initiation aids include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Ethyl Ester, Isoamyl 4-Dimethylaminobenzoate, 2-Ethylhexyl 4-Dimethylaminobenzoate, 2-Dimethylaminoethyl Benzoate, N,N-Dimethylparaformyl Aromatic amine compounds such as aniline, 4,4'-bis(dimethylamino)benzophenone (commonly called Michler's ketone), and 4,4'-bis(diethylamino)benzophenone.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid , N-naphthylglycine, naphthyloxyacetic acid and other aromatic heteroacetic acids.

The content of the photopolymerization initiator (C) is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight, based on the total amount of the binder resin (A) and the photopolymerizable compound (B).

In addition, the content of the photopolymerization start adjuvant (C-1) is preferably 0.01 to 50% by weight, more preferably 0.1 to 40% by weight, on the same basis as above.

If the total amount of the photopolymerization initiator (C) is within the above range, the sensitivity of the photosensitive resin composition becomes high, and the strength of the pixel portion formed using the above photosensitive resin composition and the smoothness of the pixel surface become better. tendency, and is therefore preferred. In addition to the above, if the amount of the photopolymerization initiation auxiliary agent (C-1) is within the above range, the sensitivity of the obtained photosensitive resin composition can be further increased. Using this photosensitive resin composition to form The productivity of the pattern substrate tends to improve, so it is preferable.

Examples of the solvent (D) used in the present invention include various organic solvents 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 dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and other diethylene glycol dialkyl ethers;

Methyl cellosolve acetate, ethyl cellosolve acetate and other ethylene glycol alkyl ether acetates;

Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc. Alkylene glycol alkyl ether acetate Esters;

Benzene, toluene, xylene, mesitylene and other aromatic hydrocarbons;

Methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones;

Ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and other alcohols;

Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and other esters;

Cyclic esters such as γ-butyrolactone, etc.

Among the above-mentioned solvents, it is preferable to use organic solvents having a boiling point of 100 to 200° C. among the above-mentioned solvents in view of applicability and drying properties, and it is more preferable to use alkylene glycol alkyl ether acetates, ketones, 3-ethyl alcohol, etc. Ethyl oxypropionate, methyl 3-methoxypropionate and other esters, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate Esters, methyl 3-methoxypropionate.

These solvents (D) can be used individually or in mixture of 2 or more types.

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 60 to 90% by weight, more preferably 70 to 85% by weight relative to the photosensitive resin composition. If the content of the solvent (D) is within the above range, when coating with a spin coater, slot & spin coater, slot coater (also called die coater, curtain coater), inkjet, etc. It exhibits good coating performance when coating on a device, and thus is preferable.

In the photosensitive resin composition of the present invention, additives such as fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation materials, and chain transfer agents may be used in combination as needed. (F).

Glass, silica, alumina, pigments, etc. are mentioned as said filler.

Examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, Thermoplastic resins such as polyurethane, etc.

As a pigment dispersant, commercially available surfactants can be used, such as polyketones, fluorines, esters, cationics, anionics, nonionics, amphoteric surfactants, etc. They can be used alone or with 2 Use the above in combination. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, Tertiary amine-modified polyurethanes, polyethyleneimine, etc., and there are also trade names KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflour (manufactured by Kyoei Chemical Co., Ltd.), Aftop (Eftop) (manufactured by Tecam Prodez (Toa Kem Prodaku) Co., Ltd.), Meikafake (Megafuak, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Florad (Frod, manufactured by Sumitomo 3M Co., Ltd.), Asahi Jiade (アサヒガ一ド), Saffron (Safulon, the above is manufactured by Asahi Glass Co., Ltd.), Sorospas (Soluspa, manufactured by Zeneka), Efka (EFKA, Efka Chemicals) company), PB821 (manufactured by Ajinomoto Co., Ltd.), etc.

Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

Examples of antioxidants include 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

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

As an anti-aggregation material, sodium polyacrylate etc. are mentioned, for example.

In addition, examples of the chain transfer agent include lauryl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

The photosensitive resin composition can be coated on a substrate, photocured and developed through the following steps, to form a pattern, for example. First, on a substrate (usually glass) or a pre-formed layer made of the solid content of a photosensitive resin composition, or a substrate formed with ITO (indium-tin oxide) or IZO (indium-zinc oxide) The composition is coated on top to obtain a coated photosensitive resin composition layer, and the photosensitive resin composition layer is prebaked to remove volatile components such as solvents to obtain a smooth coating film. At this time, the thickness of the coating film is usually about 1 to 6 μm. Ultraviolet irradiation is performed on the coating film thus obtained through a mask for forming a target pattern. At this time, all exposed parts are uniformly irradiated with parallel light, and the mask and substrate are placed in the correct position. In order to meet such requirements, it is preferable to use devices such as mask aligners and steppers. Then, the cured coating film is brought into contact with an alkaline aqueous solution to dissolve the non-exposed part, and then developed to obtain the desired pattern shape. The developing method may be any of a liquid flow method (液盛りmethod), a dipping method, a spraying method, and the like. In addition, the substrate can be tilted at any angle during development.

The developer used in the development after pattern exposure is usually an aqueous solution containing a basic compound and a surfactant.

The basic compound may be any of inorganic and organic basic compounds. Specific examples of inorganic basic compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, silicic acid Potassium, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia water, etc.

In addition, specific examples of organic basic compounds include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, mono Ethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, etc. These inorganic and organic basic compounds can be used alone or in combination of two or more. The concentration of the basic compound in the alkaline developing solution is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

As the surfactant in the alkaline developer, any of nonionic surfactants, anionic surfactants, and cationic surfactants can be used.

Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, and other polyoxyethylene derivatives, ethylene oxide/cyclo Propylene oxide block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene Vinylamine, etc.

Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl sulfate and sodium oleyl sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, laurylbenzene Alkylaryl sulfonates such as sodium sulfonate and sodium lauryl naphthalene sulfonate, etc.

Specific examples of cationic surfactants include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, quaternary ammonium salts, and the like.

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

The concentration of the surfactant in the alkaline developer is preferably 0.01 to 10% by weight, more preferably 0.05 to 8% by weight, and even more preferably 0.1 to 5% by weight.

After image development, washing with water is performed, and further post-baking may be performed at 150 to 230° C. for 10 to 60 minutes as necessary.

Using the photosensitive resin composition of the present invention, a pattern can be formed on a substrate or a color filter substrate through the steps described above. This pattern can be used as a photo spacer used in a liquid crystal display device. In addition, when the dry coating film is subjected to pattern-forming exposure, holes can be formed by using a photomask for forming holes, and it can be used as an interlayer insulating film. As the pattern design of the photomask, the shape, size, and pitch can be changed arbitrarily. Furthermore, when exposing the dry coating film, it is possible to perform full exposure without using a photomask and heat curing or only heat curing to form a transparent film. This transparent film is useful as a protective film and can also be used for touch panels.

By incorporating the pattern obtained in this way into a display device such as a liquid crystal display device, a display device having excellent quality can be produced with high yield.

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

The photosensitive resin composition of the present invention is suitable for forming a transparent film constituting a part of a color filter, for example, for forming a protective layer, a photo spacer, an insulating film, a protrusion for controlling liquid crystal alignment, and a film for matching a colored pattern A transparent film such as a thick coating layer can be used suitably for a color filter or a display device including the color filter.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples. In the examples, % and parts indicating content or usage-amount are based on weight unless otherwise specified.

Synthesis Example 1

In a 1L flask with a reflux cooler, a dropping funnel and a stirrer, flow nitrogen at 0.02L/min to make a nitrogen atmosphere, add 200 parts by weight of 3-methoxy-1-butanol and 105 parts by weight of acetic acid 3 - Methoxybutyl ester, heated to 70°C with stirring. Next, dissolve 55 parts by weight of methacrylic acid and 175 parts by weight of 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate in 140 parts by weight of 3-methoxybutyl acetate (the formula ( The compound represented by I-1) and the compound represented by formula (II-1) are mixed with a molar ratio of 50:50.) and 70 parts by weight of N-cyclohexylmaleimide to prepare a solution, and the solution is added dropwise The pump added dropwise to the flask kept at 70°C over 4 hours. On the other hand, 30 parts by weight of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by weight of 3-methoxybutyl acetate, and the resulting The solution was added dropwise to the flask over 5 hours using another drop pump. After the dropwise addition of the solution of the polymerization initiator was completed, it was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a copolymer having a viscosity (23° C.) of 114 mPa·s, a solid content of 32.6% by weight, and an acid value of 34.3 mg-KOH/g (Resin Aa) solution. The obtained resin Aa had a weight average molecular weight (Mw) of 13600 and a degree of dispersion of 2.54.

In addition, the viscosity of the copolymer solution was measured with a B-type 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 the GPC method.

Device: K2479 (manufactured 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 polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was made into degree of dispersion (Mw/Mn).

Example 1

<Preparation of Photosensitive Resin Composition>

40 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 5 parts of caprolactone, and Ester-modified multifunctional acrylate (KAYARAD DPCA-120 manufactured by Nippon Kayaku Co., Ltd.), 6 parts of 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1-one, 53 Parts of propylene glycol monomethyl ether acetate, 20 parts of 3-ethoxyethyl propionate, 37 parts of 3-methoxy-1-butanol and 87 parts of 3-methoxybutyl acetate to obtain a combination of photosensitive resins Object 1.

<Formation of patterns>

电阻值10Ω/sq)的基板后，进行干燥。在该玻璃基板上旋涂感光性树脂组合物1，使得以100mJ/cm²的曝光量(365nm)对感光性树脂组合物1进行曝光、显影、水洗、后焙烧各个工序后的膜厚为3.5μm，接着在电热板中，在75℃进行2钟的预焙烧。冷却后，使涂布有该感光性树脂组合物的基板和石英玻璃制的光掩膜之间的间隔为10μm，使用曝光机(TME-150RSK；トプコン公司制造)，在大气氛围气下，用100mJ/cm²的曝光量(365nm基准)进行光照射。ITO film (film thickness

A substrate with a resistance value of 10Ω/sq) was dried. The photosensitive resin composition 1 is spin-coated on this glass substrate, so that the film thickness after each process of exposing the photosensitive resin composition 1 with an exposure amount (365 nm) of 100 mJ/cm ² , developing, washing, and post-baking is 3.5 μm, followed by pre-baking at 75°C for 2 hours on a hot plate. After cooling, the distance between the substrate coated with the photosensitive resin composition and the photomask made of quartz glass was 10 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere. Light irradiation was performed at an exposure amount of 100 mJ/cm ² (365 nm basis).

In addition, as the photomask, a photomask in which the lower pattern was formed on the same plane was used.

A photomask having 5600 square light-transmitting portions (patterns) with a side length of 7 μm and an interval of 100 μm between the squares

After light irradiation, in an aqueous developer solution containing 0.12% nonionic surfactant and 0.05% potassium hydroxide, the above-mentioned coating film was immersed for 80 seconds at 23° C. for development, and was developed with an ultrasonic cleaner (frequency 38 kHz) for 20 minutes, and then post-baked in an oven at 230° C. for 20 minutes. After standing to cool, the film thickness was measured using a film thickness measuring device (DEKTAK3, manufactured by Nippon Vacuum Technology Co., Ltd.).

<Storage 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, and the container 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 calculated based on the following formula is 100%.

Viscosity change=[viscosity of photosensitive resin composition after storage at 23°C for 2 weeks]/[viscosity of photosensitive resin composition before storage]×100(%)

The smaller the change in viscosity, for example, the range of 100-103%, the better. In addition, viscosity measurement was performed as follows.

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

<Transmittance>

Except that in the above-mentioned exposure process of pattern formation, a photomask is not used and the film thickness is 2.9-3.1 μm, the same operation as above is carried out to prepare a cured film, and the film thickness is measured using a film thickness measuring device (DEKTAK3, Nippon Vacuum technology company) to measure.

Next, 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 into a transmittance at a film thickness of 3.0 μm. , it is 96.3%.

<Surface smoothness>

Except having used the photosensitive resin composition 1 and not using a photomask, the cured film was produced in the same manner as above. The obtained cured film was evaluated according to 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 evaluated as ◯, and the case where unevenness was present was evaluated as ×.

<pattern shape>

The pattern line width used in the surface smoothness measurement was measured with a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.), and it was 7.9 μm.

Observe the pattern shape from the front side. When the line width of the bottom is larger than that of the top, it is regarded as a forward taper; when the line width of the top and bottom is equal, it is regarded as a rectangle; when the line width of the bottom is smaller than that of the top, it is regarded as an inverse taper.

When the pattern shape is rectangular, image development adhesiveness tends to be improved, so it is preferable.

<Development adhesion>

In the above-mentioned pattern forming process, the substrate after development was immersed in a 1L glass beaker with 500ml of pure water, and was washed with an ultrasonic cleaner (US-4, measurement frequency: 38kHz, Co., Ltd.) under the condition of 23-25°C. After washing with water for 10 minutes and 20 minutes (manufactured by SND Co., Ltd.), the number of pattern-peeled objects out of 5600 pieces was counted. If the number of stripped objects is all 0, there is no stripping at all. It is generally considered that the smaller the number of peeled objects, the better the developing adhesiveness.

<Mechanical properties (total displacement and recovery rate)>

For one cured pattern obtained in the above pattern formation, the total displacement (μm) and the elastic displacement (μm) were measured using a dynamic ultra-micro hardness tester (DUH-W201; manufactured by Shimadzu Corporation), And calculate the response rate (%).

-Measurement conditions-

Test method: Load-load removal test

Test force: 20mN

Load speed: 4.4mN/s

Hold time: 5s

Indenter: truncated conical indenter (diameter 50μm)

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

As mechanical properties, it is generally considered that a pattern with a total displacement of 0.90 μm or more and a recovery rate of 45% or more is good when the film thickness is 3-5 μm and the line width is 7-10 μm.

<Solvent resistance>

Except not having used the photomask in the exposure process of said pattern formation, the same operation was performed, the coating film was prepared, and the film thickness and transmittance were measured. The prepared coating film was immersed in N-methylpyrrolidone at 30° C. for 30 minutes, the film thickness and transmittance after immersion were measured, and the change was obtained from the following formula.

Film thickness change (%): (film thickness after immersion (μm)/film thickness before immersion (μm))×100

Transmittance change (%): (transmittance after dipping (%)/transmittance before dipping (%))×100

It is generally considered good when the film thickness change and the transmittance change are 90-103%, respectively.

Solvent Resistant Adhesion:

On the coating film dipped in the solvent resistance test, 100 squares with a side length of 1 mm were cut out using a commercially available knife. A peeling test was performed using a commercially available glass ribbon, and evaluation was performed according to the following numerical values.

[(Number of squares remaining on the substrate without peeling off)/100]

It is generally considered that the higher the numerical value is, the better the adhesiveness is.

<Heat resistance>

Except not having used the photomask in the exposure process of the said pattern formation, it carried out similarly, and produced the coating film. The prepared coating film was left to stand in a clean oven at 240° C. for 1 hour, and the film thickness and transmittance (measurement wavelength: 400 nm) before and after heating were measured, and their changes were obtained from the following formula. As a result, the change in film thickness was 92.4%. In addition, 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

It is generally considered good when the film thickness change and the transmittance change are 90-103%, respectively.

Heat-resistant adhesion: 100 squares with a side length of 1 mm were cut out on the coating film heated in the heat resistance test using a commercially available knife. A peeling test was performed using a commercially available glass ribbon, and evaluation was performed according to the following numerical values.

[(Number of squares remaining on the substrate without peeling off)/100]

It is generally considered that the higher the numerical value is, the better the adhesiveness is.

Table 1

Example 2

From the composition shown in Table 1, the photosensitive resin composition 2 was obtained similarly to Example 1, and it evaluated. The results are shown in Table 2.

Example 3

From the composition shown in Table 1, the photosensitive resin composition 3 was obtained similarly to Example 1, and it evaluated. The results are shown in Table 2.

Comparative example 1

From the composition shown in Table 1, the photosensitive resin composition 4 was obtained similarly to Example 1, and it evaluated. The results are shown in Table 2.

Table 2

As can be seen from the results of Examples 1 to 3 shown in Table 2, if the photosensitive resin composition of the present invention is used, even when a fine pattern is formed, a pattern excellent in developing adhesiveness can be formed, so the process limit is wide. . In addition, a pattern and a coating film excellent in 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 did not contain the compound of 120-400 g/eq of unsaturated double bond equivalents could only obtain the pattern and coating film which developed adhesiveness deteriorated.

Industrial availability

The photosensitive resin composition of the present invention is excellent in storage stability, and can form patterns and coating films with excellent pattern shape, surface smoothness, mechanical properties, heat resistance, and solvent resistance, and can be suitable for forming protective layers, optical spacers, etc. Transparent films used in display devices, such as materials, insulating films, protrusions for liquid crystal orientation control, and coating layers for matching the film thickness of colored patterns.

Claims (5)

1. photosensitive polymer combination, wherein contain adhesive resin (A), optical polymerism compound (B), Photoepolymerizationinitiater initiater (C) and solvent (D), this adhesive resin (A) be unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A1), aliphatics polycycle epoxy compound (A2) and be different from (A1) and (A2) can with (A1) and (A2) multipolymer of the monomer of copolymerization (A3), and optical polymerism compound (B) contains the compound that the unsaturated double-bond equivalent is 120-400g/eq.

2. photosensitive polymer combination according to claim 1, wherein the unsaturated double-bond equivalent is that the compound of 120-400g/eq is the compound shown in the formula (BA),

In the formula (BA), R ^a-R ^fRepresent any group shown in hydrogen atom or the formula (BA-1)～(BA-3) respectively independently,

R ^a-R ^fIn at least four groups are any groups shown in the formula (BA-1)～(BA-3), R ^a-R ^fIn at least one group be the group shown in formula (BA-2) or the formula (BA-3).

3. photosensitive polymer combination according to claim 1 and 2, the monomer (A2) that wherein has aliphatics polycycle epoxy radicals are at least a compounds that is selected from the compound shown in compound shown in the formula (I) and the formula (II),

In formula (I) and the formula (II), R represents independently that respectively hydrogen atom or unsubstituted carbon number are the alkyl of 1-4 or are the alkyl of 1-4 by the carbon number that hydroxyl replaces,

X represents singly-bound respectively independently or contains or do not contain the alkylidene that heteroatomic carbon number is 1-6.

4. pattern, it is to use the photosensitive polymer combination put down in writing among the claim 1-3 to form.

5. a display device wherein includes the pattern of putting down in writing in the claim 4.