KR20060092092A - Photosensitive reisin composition - Google Patents

Abstract

A photosensitive resin composition containing (A) a binder resin, (B) a photo-polymerizable compound, (C) a photopolymerization initiator, (D) a solvent and a compound of formula (I):

(In formula (I), X, Y, and Z respectively independently represent a single bond, group of following formula (I-1), or group of following formula (I-2),

R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms, and R ¹ , R ² and R ³ on the same benzene ring may be the same or different. And also

R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

Photosensitive resin composition

Description

Photosensitive resin composition {PHOTOSENSITIVE REISIN COMPOSITION}

The present invention relates to a photosensitive resin composition.

Spacers are provided between the array substrate and the color filters constituting the display, such as a liquid crystal display, a touch panel, and the like, to secure a clearance between the two substrates. Regarding the formation method of such a spacer, the photo-spacer method which is a spacer formation method using the photosensitive resin composition is proposed instead of spraying the conventional spherical particle.

As a photosensitive resin composition used for formation of an optical spacer, unsaturated carboxylic acid and / or unsaturated anhydride carboxylic acid (al), an epoxy-group containing unsaturated compound (a2), and other than (al) and (a2) mentioned above Compositions containing a copolymer having a structural unit derived from an olefinically unsaturated compound (a3) are known. It has been disclosed that the spacer can be obtained by crosslinking of the carboxyl group and the epoxy group of the copolymer contained in the composition in post bake (Patent Document 1: Japanese Laid-Open Patent Publication (JP-A) No. 11-133600, Left column 2 rows of the second side to left column 9 rows of the second side).

As a composition having excellent heat resistance and plating liquid resistance, a radiation-sensitive composition containing a compound having two or more epoxy groups (Patent Document 2: JP-A No. 6-192389, left column 2 on the second side) Left-column 9 rows from rows 2 to 2, and a radiation-sensitive resin composition containing an epoxy compound having an epoxy equivalent of 250 or less (Patent Document 3: JP-A No. 10-319592, the left column of the second surface) Rows 2 to 2 on the left side of the second side) are known.

However, the compositions for spacer formation, described in JP-A 11-133600, have insufficient storage stability, and the radiation-sensitive resin compositions described in JP-A 6-192389 and 10-319592 are heat resistant. This is insufficient.

This invention can form the optical spacer excellent in heat resistance, and provides the photosensitive resin composition excellent in storage stability.

The inventors have studied photosensitive resin compositions which exhibit little of the above problems, and as a result, have found that photosensitive resin compositions containing a certain kind of epoxy compound can form optical spacers having excellent storage stability and excellent heat resistance. It was.

That is, the present invention provides a compound of the following formula [1] to [5].

[1] A photosensitive resin composition containing (A) a binder resin, (B) a photo-polymerizable compound, (C) a photopolymerization initiator, (D) a solvent and a compound of formula (I):

(In said Formula (I), X, Y, and Z respectively independently represent a single bond, group of following formula (I-1), or group of following formula (I-2),

R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms, and R ¹ , R ² and R ³ on the same benzene ring may be the same or different. And also

R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

[2] The total amount of the compound of formula (I), wherein the amount of the compound of formula (I) is the binder resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C) and the compound of formula (I). 0.1 to 20% by weight based on the photosensitive resin composition.

[3] The above-mentioned [1] or [2], wherein the photopolymerization initiator (C) is at least one compound selected from the group consisting of a triazine compound, an acetophenone compound, a biimidazole compound, an oxime compound and an acylphosphine oxide compound. Photosensitive resin composition.

[4] An optical spacer formed by using the photosensitive resin composition according to any one of [1] to [3].

[5] A display provided with the optical spacer according to the above [4].

The invention will be explained in detail below.

The photosensitive resin composition of this invention contains binder resin (A), a photopolymerizable compound (B), a photoinitiator (c), and the compound of general formula (I). In this photosensitive resin composition, other additives (F) may be dissolved or dispersed in the solvent (E), if necessary.

The binder resin (A) has alkali solubility, preferably at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated anhydride carboxylic acids, and the above unsaturated carboxylic acids and unsaturated anhydride carboxylic acids. Copolymers with monomers copolymerizable with at least one compound selected from the group consisting of:

Examples of one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and the like, either alone or in combination. It can be used in combination of the above.

Examples of monomers copolymerizable with one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated anhydrous carboxylic acids include unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) Acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, and the like; Esters containing alicyclic groups of unsaturated carboxylic acids such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth ) Acrylate, menthyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl ( Meth) acrylate, isoboroyl (meth) acrylate, pinanyl (meth) acrylate, tricyclododecyl (meth) acrylate, tricyclododecyloxyethyl (meth) acrylate, adamantley (meth ) Acrylate, norbornenyl (meth) acrylate, pineneyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate Agent, and the like; Unsaturated glycidyl carboxylates such as glycidyl (meth) acrylate and the like; Unsaturated oxetane carboxylates such as oxetane (meth) acrylate and the like; Single saturated carboxylates such as oligo ethylene glycol monoalkyl (meth) acrylates and the like; Aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene and the like; Vinyl carboxylates such as vinyl acetate, vinyl propionate and the like; Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and the like; N-substituted maleimide compounds such as N-phenylmaleimide, N-benzyl maleimide, N-cyclohexylmaleimide and the like.

Of these, methyl (meth) acrylate and benzyl (meth) acrylate are preferably used.

The monomers may be used alone or in combination of two or more.

The following (Al), (A2) and (A4) are copolymerized, and copolymer 1 is obtained, The produced copolymer 1 and (A3) react in the part derived from (A4) of copolymer 1, and copolymer 2 is In addition, the resulting copolymers 2 and (A5) react with the moieties produced by the reaction of (A3) and (A4) of copolymer 1 to obtain a copolymer. This copolymer is preferably mentioned as the copolymer used.

(Al); A compound having at least one skeleton and unsaturated bond selected from tricyclodecane skeleton and dicyclopentadiene skeleton in one molecule.

(A2); Unsaturated compounds copolymerizable with (Al) and (A4),

(A3); Carboxylic acid having an unsaturated bond,

(A4); A compound having an unsaturated bond and an epoxy group in one molecule,

(A5); Acid anhydride,

(Wherein (Al) to (A5) are not identical to each other).

Specific examples of the compound (A1) having one or more skeletons and unsaturated bonds selected from tricyclodecane skeleton and dicyclopentadiene skeleton in one molecule include dicyclopentyl (meth) acrylate, dicyclopentyl (meth) acrylate, dish Clofentanyloxyethyl (meth) acrylate and dicyclopentyloxyethyl (meth) acrylate. These compounds may be used alone or in combination of two or more.

Here, (meth) acrylate in this application means an acrylate and / or a methacrylate.

Specific examples of the unsaturated compound (A2) copolymerizable with (Al) and (A4) include unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth ) Acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, and the like; Esters containing alicyclic groups of unsaturated carboxylic acids such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth ) Acrylate, menthyl (meth) acrylate, cyclopentetyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mendidienyl (Meth) acrylate, isoboroyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pineneyl (meth) acrylate, etc. ; Single saturated carboxylates of glycols, such as oligo ethylene glycol monoalkyl (meth) acrylates and the like; Ester compounds containing aromatic rings of unsaturated carboxylic acids such as benzyl (meth) acrylate, phenoxy (meth) acrylate, and the like; Aromatic vinyl compounds such as styrene, α-methylstyrene, α-phenylstyrene, vinyltoluene and the like; Vinyl carboxylates such as vinyl acetate, vinyl propionate and the like; Vinyl carbide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and the like; N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide and the like. These may be used alone or in combination of two or more.

Specific examples of the carboxylic acid (A3) having an unsaturated bond include acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination of two or more. In addition to these acrylic and methacrylic acids, other carboxylic acids having unsaturated groups can be used together. Specific examples of other carboxylic acids having an unsaturated group include carboxylic acids having one or more unsaturated groups selected from other carboxylic acids having one unsaturated group such as crotonic acid, itaconic acid, maleic acid, fumaric acid and the like. In addition, carboxylic acids containing a hydroxyl group and a carboxyl group in the same molecule and having an unsaturated group can be used together, such as α- (hydroxymethyl) acrylic acid.

Specific examples of the compound (A4) having an epoxy group and an unsaturated bond in one molecule include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, β-propylglycidyl (meth) acrylate, β-methylglycidyl α-ethylacrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3-ethyl-3, 4-epoxybutyl (Meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) acrylate, glycidyl vinyl ether, and the like are preferably included. Glycidyl (meth) acrylates are mentioned.

Acid anhydride (A5) is a compound having one acid anhydride group in the molecule, specific examples of which are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene tetra Hydrophthalic acid, methyltetrahydrophthalic anhydride, trimellitic anhydride, and the like, preferably tetrahydrophthalic anhydride.

The binder resin (A) used in the present invention is a resin having alkali solubility, preferably (Al), (A2) and (A4) are copolymerized to obtain copolymer 1, and the resulting copolymer 1 and ( A3) is a copolymer obtained by reacting and copolymer 2 is obtained, and also the resultant copolymer 2 and (A5) are reacted.

First, (Al), (A2) and (A4) are copolymerized to obtain copolymer 1. This copolymerization is carried out under ordinary conditions.

In the polymerization process, the monomers and radical polymerization initiators used in the copolymerization reaction can be dissolved in a solvent, the temperature of which can be elevated while stirring for the execution of the polymerization reaction, or a monomer comprising the added radical polymerization initiator The temperature of is raised and can be dripped in a solvent under stirring. Alternatively, a radical polymerization initiator may be added in the solvent, the resulting solution may be heated, and the monomer may be added dropwise to the heated solution. The reaction conditions can be freely changed depending on the planned molecular weight.

The solvent to be used is not particularly limited, but is inert to radical polymerization, and an organic solvent commonly used may be used.

Specific examples thereof include ethyl acetate; Isopropyl acetate; Ethylene glycol monoalkyl ether acetates such as cellosolve acetate, butyl cellosolve acetate, and the like; Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, butylcarbitol acetate and the like; Propylene glycol monoalkyl ether acetates; Acetates such as dipropylene glycol monoalkyl ether acetate and the like; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methylcarbitol, ethylcarbitol, butylcarbitol and the like; Triethylene glycol dialkyl ether; Propylene glycol dialkyl ethers; Dipropylene glycol dialkyl ether; Ethers such as 1,4-dioxane, tetrahydrofuran and the like; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like; Hydrocarbons such as benzene, toluene, xylene, octane, decane and the like; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solution naphtha, and the like; Lactates such as methyl lactate, ethyl lactate, butyl lactate and the like; Dimethylformamide; N-methylpyrrolidone; Etc. are included.

Such solvents may be used alone or in combination of two or more.

The amount of the solvent used is 30 to 1000 parts by weight, preferably 50 to 800 parts by weight based on 100 parts by weight of the copolymer. Within this range, preferably, the molecular weight is easily controlled.

The radical polymerization initiator to be used is not particularly limited but may be capable of initiating radical polymerization, and organic peroxide catalysts and azo compounds which are commonly used may be used, and ketone peroxides, peroxy ketals, hydroperoxides, diallyl pers Mention is made of known compounds which can be classified as oxides, diacyl peroxides, peroxy esters and peroxy dicarbonates, azo compounds.

Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy-2 Ethyl hexanoate, t-hexyl peroxy-2-ethyl hexanoate, 1,1-bis (t-butyl peroxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2, 5-bis (t-butyl peroxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t- Butylcyclohexyl) peroxy dicarbonate, diisopropyl peroxy dicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butyl Peroxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexyl peroxy) 3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azo Bis amides, and the like carboxylic Bonnet.

It is preferable to select a radical polymerization initiator having a suitable half life according to the polymerization temperature. The amount of the radical polymerization initiator to be used is usually 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight based on 100 parts by weight of the total amount of the monomers used in the copolymerization reaction.

The proportion of the constituents derived from each component is preferably in the following ranges in terms of mole fractions based on the total moles of constituents constituting the copolymer 1 above.

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

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

 Structural units derived from (A4): 3 to 65 mol%

More preferably, the ratio of the said component is the following range.

 Structural units derived from (Al): 5 to 35 mol%

 Structural units derived from (A2): 5 to 80 mol%

 Structural units derived from (A4): 15 to 60 mol%

When the above constituent ratio is within the above range, the balance between flexibility and heat resistance is excellent, and a preferable backbone polymer is obtained.

Next, (A3) is added to the copolymer 1 to impart light / heat curability to the binder resin (A).

The reaction of copolymer 1 and (A3) can be carried out, for example, under the conditions described in JP-A 2001-89533. Specifically, a solution of copolymer 1 (a solution obtained by copolymerization of (Al), (A2) and (A4) may be used as it is in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube). And heated to 120 ° C. under air atmosphere while stirring the solution. (A3), trisdimethylaminomethylphenol and hydroquinone were added to the aged solution, the reaction was continued at 120 ° C. for 6 hours, and terminated when the solid acid value reached 0.8, resulting in light / thermal curability Obtained copolymer 1 is obtained.

The addition amount of (A3) is usually 5 to 100 mol%, preferably 10 to 95 mol% based on the epoxy group (derived from the A4 component) in the resin obtained by copolymerization of (Al), (A2) and (A4). to be.

When the composition ratio of (A4) is within the above range, sufficient photocurability and thermosetting are obtained, and preferably excellent reliability is provided.

Next, the said copolymer 2 and (A5) are made to react, and the binder resin (A) to which alkali solubility was provided is manufactured.

The reaction of copolymer 2 and (A5) can be carried out, for example, under the conditions described in JP-A 2001-89533. (A5) and triethylamine are added to the copolymer 2 and reacted at 120 DEG C for 3.5 hours to obtain an alkali-developable binder resin (A).

The addition amount of (A5) is 5-100 mol%, Preferably it is 10-95 mol% based on the mole number of the alcoholic hydroxyl group (derived from A3 component) of copolymer 2.

The weight average molecular weight based on the polystyrene calibration curve of the said binder resin (A) becomes like this. Preferably it is 3000-100000, More preferably, it is 5000-30000.

When the weight average molecular weight of the binder resin (A) is within the above range, its applicability is excellent, the film reduction does not easily occur during development, and also the penetration property of the non-pixel portion during development is excellent. There is this.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When molecular weight distribution exists in the said range, Preferably developability is excellent.

The content of the binder resin (A) used in the photosensitive resin composition of the present invention is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, based on the solids content of the photosensitive resin composition. to be. When the content of the binder resin (A) is within the above range, preferably, the decomposability in the developer is sufficient, the developing residue is not easily formed in the non-pixel portion on the substrate, and the film in the exposed pixel portion during development The reduction does not easily occur, and the penetration property in the non-pixel portion tends to be excellent.

As the binder resin (A), a binder resin obtained by introducing a (meth) acryl group into the side chain of the binder resin can also be used, for example, a compound containing an epoxy group and a (meth) acryl group in one molecule of a binder resin having a carboxyl group. And a resin obtained by reaction with.

As the photopolymerizable compound (B) contained in the photosensitive resin composition of the present invention, a monofunctional monomer, a difunctional monomer and a polyfunctional monomer are mentioned.

Specific examples of monofunctional monomers include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroli Money, etc.

Specific examples of difunctional monomers include 1,6-hexane diol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol Bis (acryloyloxyethyl) ether of A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of the polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, the reaction product of pentaerythritol tri (meth) acrylate with an acid anhydride, the reaction product of dipentaerythritol penta (meth) acrylate with an acid anhydride, and the like.

Among them, non- (bi-) or more polyfunctional monomers such as bifunctional monomers, polyfunctional monomers, and the like are preferably used.

Examples of such commercial products are ARONIX M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M- 1960, M-8100, M-8530, M-8560, M-9050 (manufactured by Toagosei Co. Ltd.), KAYARAD TMPTA, DPHA, DPCα-20, DPCα-30, DPCα-60, DPCα-120 (Nippon Kayaku Co Ltd.), Viscoat 295, 300, 360, GPT, 3PA, 400 (manufactured by Osaka Organic Chemical industry Ltd.), and the like.

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

Examples of the photopolymerization initiator (C) contained in the photosensitive resin composition of the present invention include acetophenone series, biimidazole series, oxime series, triazine series compounds and the like.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1 -phenylpropane-1 -one, benzyl dimethyl ketal, 2-hydroxy-1-[4- (2-hydroxy Ethoxy) phenyll-2-methylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2 -Benzyl-2-dimethylamino-l- (4-morpholinophenyl) butane-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-morpholi Nophenyl) -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-l- (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-l- (4-morpholinophenyl)- Butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-l- (4 -Morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-l- (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-l- (4- Morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo- 4-M Sibenzyl) -2-dimethylamino-l- (4-morpholino phenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (l-methylvinyl) phenyl] propane-one-one Oligomers and the like.

Examples of such non-imidazole compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl bi-imidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4'5,5'-tetraphenyl bi-imidazole (see, eg, JP-A 6-75372, 6-75373, etc.), 2,2'-bis (2 -Chlorophenyl) -4,4'5,5'-tetraphenyl bi-imidazole, 2,2'-bis (2-chlorophenyl) -4,4'5,5'-tetra (alkoxyphenyl) non- Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) bi-imidazole, 2,2'-bis (2-chlorophenyl)- 4,4 ', 5,5'-tetra (trialkoxyphenyl) bi-imidazole (see, eg, JP-B 48-38403, JP-A 62-174204, etc.), 4,4' Imidazole compounds in which the phenyl group at the 5,5'-position is substituted with a carboalkoxy group (see, for example, JP-A No. 7-10913, etc.) and the like, and preferably 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenyl Imidazole is mentioned.

Examples of the oxime compound include O-ethoxycarbonyl-α-oxymino-1-phenylpropane-1-one, a compound of formula (a), a compound of formula (b), and the like.

Examples of the triazine-based compound include 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-l, 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 (trimethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyll-1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Photopolymerization initiators commonly used in the art may be used together to the extent that the effects of the present invention are not impaired. Examples of the photopolymerization initiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, and anthracene compounds. Etc. are included.

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

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert- Butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like. This includes.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9, lO-diethoxyanthracene, and the like. .

Additionally, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxy Photopolymerization initiators such as latex, titanocene compounds and the like.

Japanese patent application issued as a photopolymerization initiator having a group capable of causing chain transfer (Public) The ones described in 2002-544205 may also be used.

Examples of the photopolymerization initiator having a group capable of inducing chain transfer include compounds of the following formulas (2) to (7).

Photopolymerization initiators having groups capable of inducing chain transfer can be used as constituent (A2) of copolymer 1. The binder resin (A) obtained using (A2) can be used together in the binder resin of the present invention.

Photopolymerization initiation aid (C-1) can be used in combination with photopolymerization initiator. As a photoinitiator, the following amine compound and carboxylic acid compound are preferable, and an aromatic amine compound is more preferable as an amine compound.

Specific examples of the photopolymerization initiation aid (C-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, and the like; Methyl 4-dimethylamino benzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl p Aromatic amine compounds such as toluidine, 4,4'-bis (dimethylamino) benzophenone (common name; ketone of Michier), 4,4'-bis (diethylamino) benzophenone and the like; Phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine And carboxylic acid compounds such as aromatic heteroacetic acids such as phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

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

When photopolymerization initiation aid (C-1) is used, its content is preferably 0.1 to 50% by weight, more preferably 0.1 to 40% by weight based on the above criteria.

When the content of the photopolymerization initiator (C) is within the above range, preferably the photosensitive resin composition has high sensitivity, and the intensity of the pixel portion formed by using the photosensitive resin composition and the flatness of the pixel surface are excellent. There is a tendency to lose. In addition, when the content of the photopolymerization initiation assistant (C-1) is within the above range, the resulting photosensitive resin composition preferably has higher sensitivity, and the productivity of the patterned substrate formed using the photosensitive resin composition increases. There is a tendency.

The photosensitive resin composition of this invention contains the compound of general formula (I). By using the compound of general formula (I), it becomes possible to form the optical spacer excellent in storage stability and heat resistance. In addition, the formed optical spacer has good solvent resistance and surface flatness, and has a recovery ratio. Excellent too.

(In said Formula (I), X, Y, and Z respectively independently represent a single bond, group of following formula (I-1), or group of following formula (I-2),

R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms, and R ¹ , R ² and R ³ on the same benzene ring may be the same or different. There is,

R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

As X, Y and Z, a single bond or a group of the formula (I-2) is preferably mentioned.

As R ¹ to R ³ , a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are preferably mentioned.

As R ⁴ to R ⁶ , hydrogen atoms, methyl groups, ethyl groups, n-propyl groups and isopropyl groups are preferably mentioned.

As the compound of the formula (I), preferably at least two of X, Y and Z represent a single bond, R ¹ to R ³ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ to R ⁶ are Reference is made to compounds which represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably two of X, Y and Z represent a single bond, the other represents a group of the formula (I-2) above and R ¹ to R Reference is made to compounds in which ³ represents a hydrogen atom and R ⁴ to R ⁶ represent a hydrogen atom.

2- [4- (2,3-epoxypropoxy) phenyl] -2 usable as the compound of formula (I), for example, as Techmore (registered trademark) VG31O1L (manufactured by Mitsui Chemical Co., Ltd.). -[4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane and the like.

The content of the compound of formula (I) is preferably 0.1 to 20 in terms of weight fraction based on the total amount of binder resin (A), photopolymerizable compound (B) photopolymerization initiator (C) and compound of formula (I). % By weight, more preferably 0.2 to 15% by weight.

When the content of the compound of formula (I) is within the above range, preferably, the chemical resistance of the pixel portion and the coated film formed using the photosensitive resin composition tends to be excellent, and the heat resistance also increases.

The photosensitive resin composition of this invention contains a solvent (D). As such a solvent (D), various organic solvents used in the photosensitive resin composition field can be used.

Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and the like; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and the like; Ethylene glycol alkyl ether acetates such as methylcellosolve acetate, ethylcellosolve acetate, and the like; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate and the like; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and the like; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and the like; Esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like; cyclic esters such as γ-butyrolactone and the like.

Among the solvents, organic solvents having a boiling point of 100 to 200 ° C. are preferably mentioned, more preferably alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate, methyl 3-methoxy Propionate and the like are mentioned and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxy in the solvent in view of applicability and dryness. Propionates are also preferably mentioned.

These solvents (D) can be used individually or in combination of two or more individually.

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 in terms of weight fraction based on the photosensitive resin composition. When the content of the solvent (D) is within the above range, spin coater, slit & spin coater, slit coater (also called die coater, curtain flow coater), When applied through an application device such as an inkjet, the applicability tends to be excellent.

In the photosensitive resin composition of the present invention, additives (F) such as fillers, other high molecular compounds, surfactants, close adherence promoters, antioxidants, ultraviolet absorbents, flocculants, chain transfer agents and the like may also be used if necessary. Can be.

Examples of the filler include glass, silica, alumina and the like.

Examples of other high molecular compounds include curing resins such as maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. have.

As the surfactant, commercially available surfactants can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic, nonionic, amphoteric surfactants, and the like, which are single or two or more. It can be used in combination. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, and further, : KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoi Kagaku KK), Eftop (manufactured by Tohkem Products Co.), Megafack (manufactured by Dainippon Inc & Chemicals Inc.), Florad (manufactured by Sumitomo 3M), Asahi guard, Surfron (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Zenca), EFKA (manufactured by EFKA CHEMICALS), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

Specific examples of the precision adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercapto Propyltrimethoxysilane and the like.

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

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

Specific examples of flocculants include sodium polyacrylate and the like.

Specific examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene and the like.

The photosensitive resin composition of this invention uses the resin component (unsaturated carboxylic acid and / or unsaturated anhydride carboxylic acid (al), epoxy group containing unsaturated group (a2), and said (al) and (a2) which were described in patent document 1). Copolymer) having a structural unit derived from the olefin unsaturated compound (a3) except for the above, and preferably, the rate of change of the viscosity after storage based on the viscosity before storage is reduced.

It is preferable that the photosensitive resin composition of this invention does not contain coloring agents, such as a pigment, when used for formation of a transparent coating film.

The photosensitive resin composition can be applied, for example, to a substrate, photocured and developed to form a pattern, as described below. First, this composition is applied on a substrate, such as glass, or on a substrate, such as a layer consisting of a solid component of a preformed photosensitive resin composition. Application is carried out using known devices such as spin coaters, slit coaters, curtain flow coaters, bar coaters and the like to form a layer of photosensitive resin composition.

The layer of photosensitive resin composition formed by the application is pre-baked to remove volatile components such as solvents and the like, to provide a flat coating film. The thickness of this coating film is about 1-6 micrometers normally. The coating film thus obtained is irradiated with ultraviolet rays through a mask for intended pattern formation (patterned exposure), and in this process, before exposure using a device such as a micro aligner, a stepper, or the like. It is desirable to allow the area to be irradiated uniformly with parallel beams and to precisely adjust the position of the mask and the position of the substrate.

Further, after that, the coating film after completion of exposure is brought into contact with the aqueous alkali solution so that the non-exposed portion is dissolved and development is performed, thereby obtaining the intended pattern form. The developing method may be any of a puddle method, a dipping method, a spray method, and the like. In addition, the substrate may be inclined at any angle during development. After development, washing with water is performed, and if necessary, post-baking for 10 to 60 minutes at 150 to 230 ° C. can also be performed. By post-baking, the curing reaction proceeds further, and reliability in making a display can be given.

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

The alkali compound can be any of inorganic and organic alkali compounds. Specific examples of the inorganic alkali compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate , Potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

Specific examples of the organic alkali compound include tetramethyl ammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropyl Amines, diisopropylamine, ethanolamine and the like. Inorganic and organic alkali compounds may be used alone or in combination of two or more. The concentration of the alkali compound in the alkaline developer is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

The surfactant in the alkaline developer may be any of nonionic surfactants, anionic surfactants and cationic surfactants.

Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers and other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylenealkyl amines, and the like.

Specific examples of nonionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfo Alkyl aryl sulfonates such as acetates and sodium dodecylnaphthalenesulfonate, and the like.

Specific examples of cationic surfactants include amine salts such as stearylamine hydrochloride and lauryltrimethyl ammonium 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, still more preferably 0.1 to 5% by weight.

The optical spacer pattern may be formed on the substrate or the color filter substrate through the application, drying and patterning exposure and development of the resulting dried coating film, as described above.

Color filters produced using the photosensitive resin composition of the present invention show a slight difference in film thickness on a plane, for example, when the film thickness is 1 to 6 μm, the difference in film thickness on the plane is 0.15 μm or less, more Furthermore, it can be controlled to 0.05 μm or less. Therefore, the color filter thus obtained is excellent in flatness, and by using it for a color liquid crystal display, a liquid crystal display of excellent quality can be produced in high yield.

The photosensitive resin composition of this invention shows the outstanding storage stability, and the optical spacer formed using the photosensitive resin composition has the outstanding heat resistance. The optical spacer formed using the said photosensitive resin composition is also excellent in solvent resistance and surface flatness, and has the outstanding recovery rate.

Example

In the following Examples, the present invention will be described in more detail, but the present invention is not limited to these Examples. Numerical values in the examples are by weight unless otherwise indicated.

Synthesis Example 1

The structural unit of binder resin Aa used in Example 1, Comparative Example 1, and Comparative Example 2 is represented by the following general formula (X).

Meaning of constituent units

a: Corresponding to the structural unit derived from (A1) in the copolymer 1.

b: It corresponds to the structural unit derived from (A2) in the copolymer 1.

c: It corresponds to the structural unit derived by reaction of the structural unit derived from (A4), and (A3) in the copolymer 1.

d: Corresponds to the structural unit derived by the reaction between the moiety attributed to (A3) and (A5) in the copolymer 2.

The molar ratio of the structural units a to d in the resin Aa, R ² , the weight average molecular weight based on the polystyrene calibration curve of the obtained resin Aa and the molecular weight distribution thereof are shown in Table 1.

The number average molecular weight (Mn) of the binder polymer and the weight average molecular weight (Mw) based on the polystyrene calibration curve were measured under the following conditions using the GPC method.

Device; HLC-8120 GPC (manufactured by Tosoh Corp.)

column; TSK-GELG 4000 HXL (brand name) + TSK-GELG 2000 HXL (brand name) (continuous connection)

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 ml / mm

Injection amount; 50 μl

Detectors; RI

Measurement sample concentration; 0.6 wt% (solvent; THF)

Reference material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, α-2500, α-500 (above brand name) (product made by Tosoh Corp.)

The ratio of the weight average molecular weight based on the polystyrene calibration criteria to the number average molecular weight obtained in the above measuring method was the molecular weight distribution (Mw / Mn).

Synthesis Example 2

In the same manner as in Synthesis Example 1 of JP-A 11-133600, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of di Ethylene glycol methyl ether was fed. Subsequently, 30 parts by weight of styrene, 20 parts by weight of methacrylic acid and 50 parts by weight of glycidyl methacrylate were fed, purged with nitrogen, and then stirring was started slowly. The solution was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing the resin Ab. The weight average molecular weight based on the polystyrene calibration criteria of the produced resin Ab was 24,000.

Example 1

[Production of Photosensitive Resin Composition 1]

50 parts (in terms of solids) of the obtained resin Aa, 50 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), 3 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (Irgacure 369 (trade name); manufactured by Ciba Specialty Chemicals), 1 part 4,4 '-(N, N-diethylamino) -benzophenone (EAB-F (trade name) Manufactured by Hodogaya Chemical Co., Ltd.) and 5 parts of Techmore VG-3101L (trade name) (manufactured by Mitsui Chemical Co., Ltd.) (2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane) was added to 173 parts of propylene glycol monomethyl ether acetate and 24 parts of 3-ethoxyethyl propio It melt | dissolved in the nate and obtained the photosensitive resin composition 1.

[Formation of optical spacer and cured resin film]

Two square inch glass substrates (# 1737; manufactured by Corning Corp.) were washed successively with neutral detergent, water and alcohol, and then dried. On this glass substrate, the photosensitive resin composition 1 was applied using the spin coater, and after application, the glass substrate was left on a hot plate without shaking and prebaked at 100 ° C. for 3 minutes. After cooling, the substrate to which the photosensitive resin composition was applied and the quartz glass photomask (the transparent portions formed by 20 square micrometers were arranged so that the distance between the adjacent squares were 100 micrometers) were spaced at an interval of 50 micrometers under an air atmosphere. Irradiation was carried out at an exposure of 100 mJ / cm ² using an ultrahigh pressure mercury lamp (USH-250D; manufactured by Ushio Inc.). Thereafter, the substrate to which the photosensitive resin composition was applied was developed by immersing in a developer at 23 ° C. (an aqueous solution containing 0.12% by weight of nonionic surfactant and 0.05% by weight of potassium hydroxide) for 80 seconds, and washed with water. Post-baking at 220 ° C. for 30 minutes gave an optical spacer. The thickness of the resultant optical spacer was measured using a film thickness meter (Dektak3; manufactured by ULVAC Inc.) to obtain a numerical value of 3.0 mu m.

Separately, a cured resin film was obtained in the same manner as described above except that no photomask was used in the exposure.

[Storage Stability of Photosensitive Resin Composition]

Immediately after preparation, the viscosity of the photosensitive resin composition 1 was measured using a viscometer (E-type viscometer; manufactured by Toki Sangyo K.K.). The same photosensitive resin composition 1 was stored at 23 ° C. for 2 weeks, and after storage the viscosity was measured in the same manner. The viscosity change rate was calculated by dividing the viscosity after storage by the viscosity before storage.

Viscosity change rate (%) = (viscosity after storage / viscosity before storage) × lOO

The results are shown in Table 3. When the viscosity change rate is close to 100%, for example, in the range of 100 to 103%, the result is excellent.

[Heat resistance]

The resulting cured resin film was placed in an oven at 240 ° C. for 1 hour, and then a penetration ratio (measured wavelength: 400 nm) per film thickness of 3.0 μm was measured. The results are shown in Table 3. The higher the penetration ratio, the better the heat resistance.

[NMP tolerance]

NMP resistance; The thickness of the resulting cured resin film was measured. The cured resin film was immersed in N-methylpyrrolidone (30 ° C. × 30 min), the film thickness after immersion was measured, and the thickness change rate was calculated from the film thickness before and after immersion. The results are shown in Table 3.

Film thickness change rate (%) = (film thickness after immersion (μm) / film thickness before immersion (μm) x lOO

When the film thickness change rate approaches 100%, the result is excellent.

[Surface flatness]

The surface of the board | substrate was visually observed at the angle of 45 degrees, and when glossiness was confirmed, it evaluated as (circle), and when glossiness was not confirmed or white turbidity (opacity) was confirmed as X. The results are shown in Table 3.

[20 μm pattern resolution]

The area | region of a 20 micrometer pattern part was observed using the scanning electron microscope (S-4100, Hitachi, Ltd. make).

When the pattern was dissolved, it was evaluated as ○, and when the pattern was not dissolved, it was evaluated as X. The results are shown in Table 3.

[Restore rate]

The total change amount (µm) and the elastic change amount (µm) were measured using a dynamic ultra-micro hardness tester (DUH-W2O1S; manufactured by Shimadzu Corp.) under the following conditions, and the recovery rate was calculated from the resulting numerical values. The results are shown in Table 3.

Test Mode: Loading-Unloading Test

Test load: 5 gf (SI unit equivalent: 0.049 N / S)

Load speed: 0.45 gf / s (SI unit equivalent: 0.0044 N)

Retention time: 5 seconds

Indenter: Conical indenter (diameter: 50 ㎛φ)

Recovery rate (%) = (elastic change amount (μm) / total change amount (μm)) × lOO

Comparative Example 1

The photosensitive resin composition 2 corresponding to the invention described in Patent Document 2 was obtained with the composition shown in Table 2 and evaluated in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 2

The photosensitive resin composition 3 corresponding to the invention described in Patent Document 2 was obtained with the composition shown in Table 2 and evaluated in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 3

The photosensitive resin composition 4 corresponding to the invention described in Patent Document 1 was obtained with the composition shown in Table 2. When the storage stability was measured in the same manner as in Example 1, the viscosity increased. As a result, subsequent evaluations were discontinued.

The compound composition of the photosensitive resin composition in an Example and a comparative example is shown in Table 2.

* 1: o-cresol novolac type epoxy resin epoxy equivalent: 195 g / eq

* 2: Bisphenol-A type epoxy resin epoxy equivalent: 189 g / eq

* 3: epoxy equivalent: 210 g / eq

The resulting cured resin film and cured resin pattern were measured in the following items, and the results are shown in Table 3.

The photosensitive resin composition in Example 1 containing the compound of formula (I) according to the present invention has excellent storage properties, and the optical spacer formed using the composition has excellent heat resistance, NMP resistance, surface flatness and recovery rate. It can be seen that the photosensitive resin compositions in Comparative Examples 1 and 2, which do not contain a compound of the formula (I), are poor in heat resistance and NMP resistance.

Industrial applicability

The photosensitive resin composition of the present invention can be used for the formation of an optical spacer in a display, and in addition, an insulating film (contact hole formation), an overcoat (flat film), a protruding material for controlling the liquid crystal alignment, and further a sealing agent It can also be used for formation.

Claims (5)

A photosensitive resin composition containing (A) a binder resin, (B) a photo-polymerizable compound, (C) a photopolymerization initiator, (D) a solvent and a compound of formula (I):

(In said Formula (I), X, Y, and Z respectively independently represent a single bond, group of following formula (I-1), or group of following formula (I-2),

R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms, and R ¹ , R ² and R ³ on the same benzene ring may be the same or different. There is, R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). A compound according to claim 1, wherein the content of the compound of formula (I) is 0.1 based on the total amount of the binder resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C) and the compound of formula (I). To 20% by weight of the photosensitive resin composition. The photosensitive resin composition of Claim 1 or 2 whose photoinitiator (C) is one or more compound chosen from the group which consists of a triazine compound, an acetophenone compound, a biimidazole compound, an oxime compound, and an acylphosphine oxide compound. A photo-spacer formed using the photosensitive resin composition according to any one of claims 1 to 3. Display provided with the optical spacer according to claim 4.