KR100911076B1 - Photosensitive resin composition and spacer for liquid crystal panel - Google Patents

Abstract

The photosensitive resin composition which can form the adhesive liquid crystal panel spacer with high adhesiveness, and the liquid crystal panel spacer formed from the said photosensitive resin composition are provided.

The photosensitive resin composition of this invention is a photosensitive resin composition containing (A) photopolymerizable compound, (B) photoinitiator, and (C) adhesion promoter, The said (C) component is a silane compound which has group containing a nitrogen atom. It is characterized by having one or less hydrogen atoms couple | bonded with the said nitrogen atom, It is used suitably for formation of the spacer for liquid crystal panels.

Liquid crystal panel, spacer, photosensitive resin, photoinitiator, adhesion promoter, silane

Description

Photosensitive resin composition and spacer for liquid crystal panel {PHOTOSENSITIVE RESIN COMPOSITION AND SPACER FOR LIQUID CRYSTAL PANEL}

The present invention relates to a photosensitive resin composition and a spacer for a liquid crystal panel, and more particularly, a photosensitive resin composition which is very suitable for forming a spacer provided between two substrates of a liquid crystal panel, and the photosensitive resin composition. It relates to a spacer for a liquid crystal panel formed.

In the liquid crystal panel of the liquid crystal display device, since the liquid crystal material is sandwiched by a transparent substrate such as two glass substrates, a spacer is formed between the two substrates so as to fill the liquid crystal material. It is necessary to form.

Conventionally, in forming a spacer, a method of dispersing beads particles serving as spacers on the entire surface of the substrate has been employed, but beads adhere to the pixel display portion, and contrast and display image quality of an image are deteriorated. There was a problem. Therefore, in recent years, various methods of forming this spacer with the photosensitive resin composition are proposed (refer patent document 1, 2 etc.). In this method, the photosensitive resin composition is coated on a substrate, exposed through a predetermined mask and then developed, and a spacer such as a dot shape is formed, and a predetermined portion other than the pixel display portion is formed. A spacer can be formed only in a part.

[Patent Document 1] Japanese Patent Publication No. 2006-184841

[Patent Document 2] Japanese Patent Application Laid-Open No. 2006-308961

By the way, this spacer is often formed on the ITO, overcoat, or alignment film formed in the board | substrate. In some cases, it may be formed on the color filter or on the insulating film covering the TFT. Thus, although the spacer is formed on various base materials, when adhesiveness with respect to this base material is lacking, there exists a possibility that pattern peeling may occur, for example at the time of image development.

So, until now, in order to make up for the lack of adhesiveness, the development time has been shortened to cope with the problem. However, if the development time is short, problems such as occurrence of foreign matters due to poor development or irregularity of CD values due to trailing shapes have been avoided. Will occur. In particular, when the substrate size becomes large, it becomes difficult to keep the development time constant in the substrate, and it becomes difficult to respond by shortening the development time.

Therefore, as this spacer, it was desired to improve the adhesiveness itself with respect to the base material of the board | substrate in which a spacer is formed so that image development time may be long. In particular, in recent years, since the cross-sectional area of the spacer tends to be small for high precision displays, the demand for adhesion is expected to be higher.

This invention is made | formed in view of such a conventional subject, and it aims at providing the photosensitive resin composition which can form the liquid crystal panel spacer with high adhesiveness with respect to various base materials, and the liquid crystal panel spacer formed from the said photosensitive resin composition. do.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventors discovered that the said subject can be solved by containing the silane compound of a specific structure in the photosensitive resin composition, and came to complete this invention. . Specifically, the present invention provides the following.

The 1st aspect of this invention is the photosensitive resin composition containing (A) photopolymerizable compound, (B) photoinitiator, and (C) adhesion promoter, The said (C) component has the silane which has group containing a nitrogen atom ( silane) compound, and one or more hydrogen atoms couple | bonded with the said nitrogen atom are photosensitive resin compositions characterized by the above-mentioned.

The 2nd aspect of this invention is formed from the photosensitive resin composition of this invention, It is a spacer for liquid crystal panels characterized by the above-mentioned.

According to this invention, the photosensitive resin composition which can form the liquid crystal panel spacer with high adhesiveness with respect to various base materials, and the liquid crystal panel spacer formed from the said photosensitive resin composition can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. In this specification, "(meth) acrylic acid" means one or both of acrylic acid and methacrylic acid. Similarly, "(meth) acrylate" means one or both of acrylate and methacrylate.

[Photosensitive resin composition]

The photosensitive resin composition of this invention contains the (A) photopolymerizable compound, (B) photoinitiator, and (C) adhesion promoter. Hereinafter, each component contained in the photosensitive resin composition of this invention is demonstrated.

[(A) Photopolymerizable Compound]

Said (A) photopolymerizable compound (henceforth (A) component) is a substance which superposes | polymerizes and hardens | cures by irradiation of light, such as an ultraviolet-ray. As this (A) component, resin or monomer (monomer) which has an ethylenic unsaturated group is preferable, and it is more preferable to combine these. By combining the resin which has an ethylenically unsaturated group, and the monomer which has an ethylenically unsaturated group, sclerosis | hardenability can be improved and pattern formation can be made easy. In the present specification, a compound having an ethylenically unsaturated group having a mass average molecular weight of 1000 or more is referred to as "resin having an ethylenically unsaturated group", and a compound having a mass average molecular weight of less than 1000 is referred to as a "monomer having an ethylenically unsaturated group". .

<Resin having an ethylenically unsaturated group>

Examples of the resin having an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumaric acid, monoethyl fumaric acid, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, and ethylene glycol Monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri ( Ta) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythrate Oligomers polymerized by lithol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cardoepoxy diacrylate, etc .; polyester prepolymers obtained by condensation of polyhydric alcohols with monobasic or polybasic acids ( Polyurethane (meth) acrylate obtained by making (meth) acrylic acid react after polyester (meth) acrylate obtained by making (meth) acrylic acid react with a prepolymer), a polyol, and the compound which has two isocyanate groups; Type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol furnace Rock type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin, etc. Epoxy (meth) acrylate resin etc. which are obtained by making the epoxy resin of this and (meth) acrylic acid react are mentioned. Moreover, resin which made polybasic acid anhydride react with epoxy (meth) acrylate resin can be used.

Among the resins having an ethylenically unsaturated group, a copolymer (A1) having a structural unit (a1) represented by the following formula (a-1) and a structural unit (a2) having a crosslinkable group improves resolution and storage stability. It is preferable at the point which can be made.

[In formula (a-1), R <^a0> represents a hydrogen atom or a methyl group, R <^a1> represents a single bond or a C1-C5 alkylene group, R <^a2> a C1-C5 alkyl (alkyl) group (however, when R ^a2 is present in two or more, these R ^a2s may be the same as or different from each other), a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b Is 5 or less.]

R ^a0 is a hydrogen atom or a methyl group, and is preferably a methyl group.

R ^a1 is a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms. Specifically, methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, tert-butylene group, pentylene group, isopentylene group, neopentylene group, etc. are mentioned. Especially, it is preferable that they are a single bond, a methylene group, and an ethylene group. Especially in the case of a single bond, it is preferable at the point which can improve the heat resistance of the hardened | cured material obtained.

Although a shows the integer of 1-5, it is preferable that a is 1 in the point which manufacture is easy. Moreover, it is preferable that the coupling | bonding position of the hydroxyl group in a benzene ring is 4-position, when the carbon atom couple | bonded with R <^a1> is a reference | standard (1 position).

R <^a2> is a C1-C5 linear or branched alkyl group. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group and neopentyl group. Especially, since it is easy to manufacture, it is preferable that it is a methyl group or an ethyl group. In addition, b represents the integer of 0-4.

Specific examples of the structural unit (a1) include those represented by the following formulas (a-1-1) and (a-1-2). In particular, the structural unit represented by Formula (a-1-1) is preferable.

This structural unit (a1) can be introduce | transduced into a copolymer (A1) by copolymerizing the polymerizable monomer represented by following formula (a-1) 'with another polymerizable monomer.

[R <^a0> , R <^a1> , R <^a2> , a, and b are the same as the above in formula (a-1) #.]

The structural unit (a2) is a structural unit having a crosslinkable group. The crosslinkable group is crosslinked by heat, and examples thereof include an organic group containing an ethylene unsaturated group, an organic group containing an epoxy group, and an organic group containing an oxetanyl group. .

Especially, it is preferable to have an organic group containing an epoxy group from the point of being able to improve the heat resistance and strength of the hardened | cured material obtained. As such a structural unit (a2), glycidyl acrylate, glycidyl methacrylate, acrylic acid (beta) -methylglycidyl, methacrylic acid (beta) -methylglycidyl, and (alpha)-ethyl acrylate glycidyl, for example , α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, acrylic acid 3, 4-epoxybutyl, methacrylic acid-3, 4-epoxybutyl, acrylic acid-6, 7-epoxyheptyl, Methacrylic acid-6, 7-epoxyheptyl, α-ethyl acrylic acid-6, 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, And those derived from polymerizable monomers such as (3,4-epoxycyclohexyl) methyl methacrylate. These structural units (a2) can be used individually or in combination of 2 or more types.

As a particularly preferable structural unit (a2), the structural unit represented by a following formula (a-2) is mentioned. The structural unit represented by this formula (a-2) is preferable at the point which can improve the ease of manufacture, the superiority of cost, and the solvent resistance of the hardened | cured material obtained.

[R <^a3> represents a hydrogen atom or a methyl group in a formula (a-2).]

Moreover, the said copolymer (A1) may have structural units (a3) other than structural unit (a1) and (a2). This structural unit (a3) will not be specifically limited if it is a structural unit derived from the compound which has an ethylenically unsaturated group.

As such a structural unit (a3), for example, unsaturated carboxylic acids, (meth) acrylic acid ester, (meth) acrylamide, allyl compound, vinyl ether, vinyl ester, styrene, or (meth) acrylonitrile The structural unit chosen from these etc. are mentioned.

Examples of the unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid, and anhydrides of these dicarboxylic acids. Can be mentioned.

Examples of the acrylic esters include linear or branched alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate and t-octyl acrylate; Alicyclic alkyl acrylates such as hexyl acrylate, dicyclopentanyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentaoxyethyl acrylate, isobornyl acrylate; chloroethyl acrylate, 2 , 2-dimethylhydroxypropyl acrylate, 2-hydroxyethyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate , Furfuryl acrylate, te La tetrahydro furfuryl acrylate, aryl acrylate, and the like (for example, phenyl acrylate).

As methacrylic acid ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, for example. Straight or branched chain alkyl methacrylates such as acrylate, amyl methacrylate, hexyl methacrylate and octyl methacrylate; cyclohexyl methacrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl methacrylate, dicy Alicyclic alkyl methacrylates such as clofentanyloxyethyl methacrylate and isobonyl methacrylate; benzyl methacrylate, chlorobenzyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate , 5-hydroxypentyl methacrylate, 2, 2-dimethyl- 3-hydroxypropyl methacrylate, tri Thiololpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, aryl methacrylate (e.g. phenyl methacrylate, cresyl methacrylate) ), Naphthyl methacrylate), and the like.

As acrylamides, for example, acrylamide and N-alkyl acrylamide (as for carbon number of an alkyl group, 1-10 are preferable, for example, a methyl group, an ethyl group, a propyl group, a butyl group, t-butyl group, a heptyl group, and an jade) Tyl group, cyclohexyl group, hydroxyethyl group, benzyl group, etc. are mentioned, N-aryl acrylamide (Aryl group is phenyl group, tolyl group, nitrophenyl group, naphthyl group, hydroxyphenyl group, for example.) Etc.), N, N-dialkylacrylamide (The carbon number of an alkyl group is 1-10 is preferable.), N, N-arylacrylamide (A aryl group can mention a phenyl group, for example.), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc. are mentioned.

As methacrylamides, for example, methacrylamide and N-alkyl methacrylamide (carbon number of the alkyl group is preferably 1 to 10, for example, methyl group, ethyl group, t-butyl group, ethylhexyl group, Hydroxyethyl group, cyclohexyl group, etc.), N-aryl methacrylamide (as an aryl group, a phenyl group, a tolyl group, a nitrophenyl group, a naphthyl group, a hydroxyphenyl group etc. are mentioned, for example), N , N-dialkyl methacrylamide (as an alkyl group, ethyl group, propyl group, butyl group etc. are mentioned), N, N- diaryl methacrylamide (as an aryl group, a phenyl group is mentioned, for example), N-hydroxyethyl-N-methyl methacrylamide, N-methyl-N-phenyl methacrylamide, N-ethyl-N-phenyl methacrylamide, etc. are mentioned.

As the allyl compound, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate allyl) (allyl palmitate), allyl stearate, allyl stearate, allyl benzoate, allyl acetoacetic acid, allyl lactate, etc.), allyloxyethanol, and the like.

Examples of vinyl ethers include alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl). Vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylamino Ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ether (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2, 4-dichlorophenyl ether And vinyl naphthyl ether, vinyl anthranyl ether, and the like).

As vinyl esters, for example, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl Butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

As styrene, For example, styrene, alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl) Styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (for example, methoxy styrene, 4-methoxy-3-methyl) Styrene, dimethoxy styrene, and the like), halogen styrene (for example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, Fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.) are mentioned). Can be.

The structural unit (a1) in the copolymer (A1) is 10 to 80 mol% (in the case of molar ratio, (a1) :( a2) is preferably 1: 9 to 9: 1), and 20 to 80 It is more preferable that it is mol% (in the case of molar ratio, (a1) :( a2) is 2: 8-8: 2), and it is most preferable that it is 20-70 mol%. By setting it as said range, the developability of the photosensitive resin composition can be improved.

Moreover, it is preferable that it is 10-90 mol%, and, as for the structural unit (a2) in the said copolymer (A1), it is more preferable that it is 20-80 mol%. By setting it as said range, the thermosetting and chemical-resistance of the photosensitive resin composition can be improved.

Moreover, it is preferable that the structural unit (a3) in the said copolymer (A1) is 0-60 mol%, It is more preferable that it is 0-30 mol%, It is still more preferable that it is 0-10 mol%, Most preferably not included.

As for the mass mean molecular weight (Mw: measured value by styrene conversion of gel permeation chromatography (GPC)) of the said copolymer (A1), 2000-50000 are preferable, and it is more preferable that it is 5000-30000. By setting the mass average molecular weight to 2000 or more, it is possible to easily form a film, and by setting it to 50000 or less, it becomes possible to obtain appropriate developability.

The said copolymer (A1) can be manufactured by well-known radical polymerization. That is, after melt | dissolving the polymeric monomer which guides the said structural unit (a1), (a2), and (a3), and a well-known radical polymerization initiator in a polymerization solvent, it can manufacture by heat-stirring.

<Monomer having ethylenically unsaturated group>

Monomers having an ethylene unsaturated group include a monofunctional monomer and a polyfunctional monomer.

As a monofunctional monomer, (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy Methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, sheet Laconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropanesulfonic acid, tert- butyl acrylamisulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acryl Rate, 2-phenoxy-2-hydro Cipropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate , Half of glycidyl (meth) acrylate, 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoropropyl (meth) acrylate, phthalic acid derivative ( Meth) acrylate, etc. are mentioned. These monofunctional monomers can be used individually or in combination of 2 or more types.

On the other hand, as a polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di ( Meta) acrylate, butylene glycol di (meth) acrylate, neopentylglycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pen Other (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2, 2-bis (4- (meth) acryloxy diethoxyphenyl) propane, 2, 2-bis (4- (meth) acryloxy Polyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether Di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diiso) Cyanate), a reaction product of 2-hydroxyethyl (meth) acrylate, such as trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, Polyfunctional monomers, such as a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, a triacrylformal, etc. are mentioned. These polyfunctional monomers can be used individually or in combination of 2 or more types.

It is preferable that content of the monomer which has this ethylenically unsaturated group is 5-50 mass% with respect to solid content of the photosensitive resin composition, More preferably, it is the range of 10-40 mass%. By setting it as said range, it exists in the tendency to balance the sensitivity, developability, and resolution, and it is preferable.

It is preferable that content of (A) component is 5-50 mass% with respect to solid content of the photosensitive resin composition, More preferably, it is the range of 10-40 mass%. By setting it as said range, it exists in the tendency to balance the sensitivity, developability, and resolution, and is preferable.

[(B) Photoinitiator]

What is necessary is just to select the said (B) photoinitiator (henceforth (B) component) according to the kind of said (A) component.

As this (B) component, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) Phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dode Silphenyl) -2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl -1-[4- (methylthio) phenyl] -2-morpholino-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one , Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyl oxime), 2, 4, 6-trimethylbenzoyldiphenyl phos Pinoxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylamino benzoic acid, 4-dimethylamino benzoic acid , 4-dimethylamino benzoic acid ethyl, 4-dimethylamino benzoic acid butyl, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-beta -methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1, 2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoylbenzoate methyl, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2, 4- Dimethyl thioxanthone, 1-chloro-4-propoxy city oxanthone, thioxanthene, 2-chlorothioxanthene, 2, 4-diethyl thioxanthene, 2-methyl thioxanthene, 2-isopropyl thi Oxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercapto Benzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4, 5-di (m-methoxyphenyl) -imida Zolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bis-bisdimethylaminobenzophenone, 4, 4 -'- bisdiethylamino benzophenone, 4, 4 -'- dichloro benzophenone, 3, 3- dimethyl -4-methoxybenzophenone, benzil, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzo Phosphorous butyl ether, acetophenone, 2, 2-diethoxyacetophenone, p-dimethyl acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, p- Dimethylamino acetophenone, p-tert- butyl trichloro acetophenone, p-tert- butyl dichloro acetophenone, (alpha), (alpha)-dichloro- 4-phenoxy acetophenone, thioxanthone, 2-methyl thioxanthone, 2- Isopropyl thioxanthone, dibenzosuberon, pentyl-4- dimethylaminobenzo Yit, 9-phenylacridine, 1, 7-bis- (9-acridinyl) heptane, 1, 5-bis- (9-acridinyl) pentane, 1, 3-bis- (9-acridy Nil) propane, p-methoxytriazine, 2, 4, 6-tris (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2 -[2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-tri Azine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4, 6-bis ( Richloromethyl) -s-triazine, 2, 4-bistrichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2, 4-bistrichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bistrichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2 And 4-bistrichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine. Especially, it is especially preferable in terms of a sensitivity to use the oxime system photoinitiator. These (B) components can be used individually or in combination of 2 or more types.

It is preferable that content of (B) component is 0.5-30 mass% with respect to solid content of the photosensitive resin composition, More preferably, it is the range of 1-20 mass%. By setting it as said range, sufficient heat resistance and chemical-resistance can be obtained, and a film formation ability can be improved and a photocuring defect can be suppressed.

Moreover, you may combine photoinitiator with this (B) component.

Examples of the photoinitiator include triethanolamine, methyl diethanol amine, triisopropanol amine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoic acid. Ethyl hexyl, benzoic acid 2-dimethylaminoethyl, N, N- dimethyl paratoluidine, 4, 4'-bis (dimethylamino) benzophenone, 9, 10- dimethoxy anthracene, 2-ethyl-9, 10- dimethoxy anthracene , 9, 10-diethoxy anthracene, 2-ethyl-9, 10-diethoxy anthracene, etc. are mentioned. These photoinitiators can be used individually or in combination of 2 or more types.

[(C) adhesion promoter]

The said (C) adhesion promoter (henceforth (C) component) is a silane compound which has a group containing a nitrogen atom, and is a compound with one or less hydrogen atoms couple | bonded with the said nitrogen atom. As this compound, the amine silane compound which is a secondary or tertiary amine, an isocyanate silane compound, and a ketimine silane compound are mentioned, for example. By using these compounds, adhesiveness can be improved.

As said amine silane compound, the compound represented by a following formula (c-1) is mentioned, for example.

Wherein (c1) of, R ^c1 and R ^c2 represents a hydrogen atom or an organic (provided that at least one of R ^c1 and R ^c2 is an organic group.), R ^c3, R ^c4, and R ^c5 each other Independently represent an alkoxy group or an organic group having 1 to 6 carbon atoms, provided that at least one of R ^c3 , R ^c4 , and R ^c5 is an alkoxy group, and n represents an integer of 1 to 6;

As an organic group which ^concerns on said R <^c1> and R <^c2> , for example, a C1-C10 primary or secondary alkyl group, a C3-C7 cycloalkyl group, a C6-C10 aryl (aryl) group, a C7-C10 aralkyl group, etc. are mentioned. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, 2-methylbutyl group, isopentyl group, Isohexyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, tolyl group, xylyl ( and xylyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, benzyl group, α-phenethyl group, β-phenethyl group and the like. Among these, it is preferable that it is an electron donating group, and it is especially preferable that it is a phenyl group.

As an especially preferable compound among the said amine silane compounds, N-phenyl- (gamma)-aminopropyl trimethoxysilane represented by a following formula (c-1-1) is mentioned.

As said isocyanate type silane compound, the compound represented by a following formula (c-2) is mentioned, for example.

[In formula (c-2), ^Rc3 , ^Rc4 , ^Rc5 , and n are the same as the above.]

As said ketimine-type silane compound, the compound represented by a following formula (c-3) is mentioned, for example.

[In formula (c-3), ^Rc6 and ^Rc7 represent a hydrogen atom or an organic group, and ^Rc3 , ^Rc4 , ^Rc5 , and n are the same as the above.]

As an organic group which ^concerns on said R <^c6> and R <^{c7> a} C1-C10 primary or secondary alkyl group, a C3-C7 cycloalkyl group, a C6-C10 aryl group, C7-C7 10 aralkyl group etc. are mentioned. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, 2-methylbutyl group, isopentyl group, Isohexyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, tolyl group, xylyl group, mesityl group And 1-naphthyl group, 2-naphthyl group, benzyl group, α-phenethyl group, β-phenethyl group and the like.

It is preferable that content of (C) component is 0.01-0.5 mass% with respect to solid content of the photosensitive resin composition, More preferably, it is the range of 0.05-0.3 mass%. By setting it as said range, adhesiveness can be improved more.

[Organic solvent]

It is preferable that the photosensitive resin composition of this invention contains the organic solvent for the improvement of applicability | paintability, and viscosity adjustment. As this organic solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether Tripropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as lipropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and the like Other ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy -2-methyl propionic acid Methyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanoic acid Methyl, 3-methoxybutyl acetate, 3-methyl- 3-methoxybutyl acetate, 3-methyl- 3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate , I-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, butyrate n-propyl, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, Other esters such as methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetate Amides such as amide have. These solvents can be used individually or in combination of 2 or more types.

Content of the organic solvent is not specifically limited, It is suitably set according to the coating film thickness in the density | concentration which can be apply | coated to a board | substrate. 5-500 cps is preferable, as for the viscosity of the photosensitive resin composition, the range of 10-50 cps is more preferable, The range of 20-30 cps is more preferable. Moreover, 5-100 mass% is preferable, and, as for solid content concentration, the range of 20-50 mass% is more preferable.

[Other ingredients]

The photosensitive resin composition of this invention can be made to contain additives, such as a thermal-polymerization inhibitor, an antifoamer, surfactant, as needed.

As said thermal polymerization inhibitor, a conventionally well-known thing may be sufficient and a hydroquinone, a hydroquinone monoethyl ether, etc. are mentioned.

As said antifoamer, a conventionally well-known thing may be sufficient and a silicone type, a fluorine-type compound, etc. are mentioned.

As said surfactant, a conventionally well-known thing may be sufficient and compounds, such as an anionic type, a cationic type, and a nonionic type, are mentioned.

[Preparation Method of Photosensitive Resin Composition]

The photosensitive resin composition of this invention mixes (disperses and knead | mixes) each said component with stirrers, such as three roll mills, a ball mill, a sand mill, and a 5 micrometer membrane as needed. It can be prepared by filtering with a filter such as a filter (membrane filter).

[Formation method of spacer for liquid crystal panel]

Hereinafter, the method of forming the spacer for liquid crystal panels using the photosensitive resin composition of this invention is demonstrated.

First, on a substrate on which a spacer is to be formed, a contact transfer type coating device such as a roll coater, reverse coater, bar coater, spinner (rotary coating device), curtain flow, or the like Using a non-contact type coating apparatus such as a coater (curtain flow coater), the photosensitive resin composition is applied and dried to remove the solvent.

Next, through a negative mask, active energy rays of ultraviolet light and excimer laser light are irradiated and partially exposed. The light source which emits ultraviolet-rays, such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a carbon arc lamp, can be used for exposure. Although the energy dose to irradiate changes with the composition of the photosensitive resin composition, about 30-2000mJ / cm <^2> is preferable, for example.

Next, a spacer is formed by developing the photosensitive resin layer after exposure with a developing solution. The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. Specific examples of the developing solution include organic compounds such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

And post-baking is performed to the spacer after image development, and it heat-hardens. As for the temperature of a postbaking, 150-250 degreeC is preferable.

Since the adhesiveness to various base materials improves the photosensitive resin composition of this invention, when using the photosensitive resin composition of this invention at the time of forming a spacer in this way, even if it takes long developing time, pattern peeling does not occur. In other words, the development margin is long. Therefore, even when there exists a part with a thick film thickness of the photosensitive layer, such as an edge part of a board | substrate, it can reliably melt | dissolve and remove by developing long.

In addition, even when developing using the spray method, the margin for spray pressure difference in the substrate surface is improved, so the yield is improved.

Moreover, even when rubbing after forming an oriented film on a spacer, pattern peeling does not arise by rubbing.

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

<Example 1>

As the component (A), the molar ratio of the structural unit (a1) represented by the following formula (a-1-1) and the structural unit (a2) represented by the following formula (a-2-1) is 40:60 (A -1) Resin (mass average molecular weight 9000) and dipentaerythritol hexaacrylate (DPHA) were used.

As the component (B), (B-1) ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (o-acetyl oxime) (chiba Specialty Chemical Co., Ltd., IRGACURE® OXE02) was used.

As (C) component, (C-1) N-phenyl- (gamma) -aminopropyl trimethoxysilane (made by Shin-Etsu Chemical Co., Ltd., KBM573) was used.

As surfactant, BYK310 by Bekchem Japan Co., Ltd. was used.

Each said component and the organic solvent were mixed, and after stirring for 2 hours by the stirrer, it filtered by the 5 micrometer membrane filter, and the photosensitive resin composition was prepared. It shows in Table 1 about the compounding quantity of each component.

<Example 2>

As the component (C), a photosensitive resin composition was prepared in the same manner as in Example 1 except that the organic solvent was changed using (C-2) N and N-dimethyl-3-aminopropyltrimethoxysilane.

<Example 3>

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the organic solvent was changed using (C-3) N-ethyl-3-aminopropylmethyldimethoxysilane as the component.

<Example 4>

(A-1) The molar ratio of the structural unit derived from methacrylic acid, the structural unit derived from methacrylic acid glycidyl, and the structural unit derived from styrene instead of resin is 20:40:40 (A- 2) Except having used resin, it carried out similarly to Example 1, and prepared the photosensitive resin composition.

<Comparative Example 1>

The photosensitive resin composition was prepared like Example 1 except having changed the organic solvent, without using (C) component.

<Comparative Example 2>

The photosensitive resin composition was prepared like Example 1 except having changed the compounding quantity of the organic solvent using (C-4) 3-aminopropyl triethoxysilane as (C) component.

<Comparative Example 3>

The photosensitive resin composition was prepared like Example 1 except having changed the organic solvent using (C-5) 3-methacryloxypropyl triethoxysilane as (C) component.

<Comparative Example 4>

The photosensitive resin composition was prepared like Example 4 except having changed the organic solvent without using (C) component.

Solvent: MA = 3-methoxybutyl acetate

AN = cyclohexanone

PM = propyleneglycol monomethyl ether acetate

EEP = Ethoxyethyl Propionate

<Evaluation>

The adhesiveness to various base materials was evaluated using the photosensitive resin composition prepared in the said Examples 1-4 and Comparative Examples 1-4. Examples of the substrate include a glass substrate (Dow Corning Co., 1737 glass), a glass substrate with a color filter, a glass substrate with an overcoat layer, a glass substrate with an ITO layer, a glass substrate with a color filter, and poly as an alignment film. Five kinds of glass substrates in which a polyimide layer was formed were used, and the following four characters were produced as follows.

The glass substrate on which the color filter is formed is spin-coated on the 1737 glass so that a carbon dispersed black resist (CFPRKBK, manufactured by Tokyo Oka Industries Co., Ltd.) has a thickness of 1.5 μm. Coated with UV light, and exposed to 100 mJ in terms of I-line with a UV exposure apparatus (topcon), and developed at 25 degrees for 60 seconds using 0.04% KOH, followed by a postbake at 200 degrees for 30 minutes. It produced by doing. The film obtained corresponds to the black matrix of the color filter.

The glass substrate in which the overcoat layer was formed was apply | coated on the said 1737 glass so that the thermosetting overcoat liquid Optoma (made by JSR company) might be set to a film thickness of 2 micrometers, and it baked by baking in 200 degreeC for 30 minutes.

The glass substrate in which the ITO layer was formed was produced by forming 2000 kPa of ITO on the said 1737 glass so that surface resistance value might be set to 10 ohms.

The glass substrate in which the polyimide layer was formed was produced by rubbing the film | membrane formed so that it might be set to 3000 microseconds on the said 1737 glass by 3000 rotations using the rubbing cloth.

After apply | coating the photosensitive resin composition prepared by said Examples 1-4 and Comparative Examples 1-4 on each base material, it dried at 100 degreeC for 90 second, and obtained the photosensitive layer which has a film thickness of about 3 micrometers. Subsequently, the photosensitive layer was irradiated with ultraviolet rays selectively at an exposure dose of 25 mJ / cm ² through a negative mask, and a CD-150 CR (manufactured by JSR Co., Ltd.): pure water = 1: 100 was used as a developing solution. By spray development, a dot-shaped pattern was formed. The developing time was changed in the range of BP + 10 seconds to BP + 40 seconds on the basis of the time (BP: breakpoint) at which the unexposed portion was completely dissolved. Thereafter, spray cleaning with pure water was carried out and postbake was performed at 220 ° C. for 40 minutes on the formed pattern to form a dot spacer having a diameter of 20 μm.

Then, the pattern peeling did not occur at the time of development, and the spacer was able to be formed, the pattern peeling occurred in part, but the spacer could be formed, and the pattern peeling occurred and the spacer could not be formed. , The adhesiveness of the spacer was evaluated. The results are shown in Tables 2 and 3.

As can be seen from Tables 2 and 3, in Examples 1 to 4 containing a specific silane compound as the component (C), since the adhesion to various substrates is improved, the development time is extended to BP + 40 seconds. Even pattern peeling did not occur. On the other hand, in Comparative Examples 1-4 which did not contain (C) component or contained the silane compound different from this invention, pattern peeling occurred in developing time of BP + 20 second-BP + 30 second also about any base material.

Claims (8)

delete delete delete delete delete As a photosensitive resin composition containing (A) photopolymerizable compound, (B) photoinitiator, and (C) adhesion promoter, The said (C) component is a silane compound which has a group containing a nitrogen atom, one or more hydrogen atoms couple | bonded with the said nitrogen atom, Moreover, the said (C) component is an amine silane compound which is a secondary or tertiary amine, The said amine silane compound is represented by a following formula (c-1), The photosensitive resin composition characterized by the above-mentioned.

[In formula (c-1), R <^c1> and / or R <^c2> represent a phenyl group, and R <^c3> , R <^c4> , and R <^c5> represent a C1-C6 alkoxy group or organic group independently of each other, provided that R <^c3> , At least one of R ^c4 and R ^c5 is an alkoxy group.), N represents an integer of 1 to 6.] delete It formed with the photosensitive resin composition of Claim 6, The spacer for liquid crystal panels characterized by the above-mentioned.