TWI422970B - Photosensitive resin composition, spacer and liquid crystal display device having thereof - Google Patents

Description

Photosensitive resin composition, interstitial body, and liquid crystal display element including the same

The present invention relates to a photosensitive resin composition, a spacer, and a liquid crystal display element therewith, and more particularly to a photosensitive resin composition having high sensitivity in a weak exposure process of a halftone mask. And a spacer body having an upright profile and a liquid crystal display element having the spacer body.

In the process of the conventional liquid crystal display, in order to keep the two glass substrates at a fixed interval, glass beads or plastic beads are usually spread between the two glass substrates. Since the beads scattered by the conventional method are scattered, if they are inadvertently distributed to the red (R), green (G), and blue (B) pixels, the scattering of incident light is easily caused, thereby lowering the liquid crystal display. Contrast.

In order to improve the above problems, a photosensitive resin type spacer is generally produced by a lithography process. The photosensitive resin type spacer obtained by the method forms a dot-like or straight strip-shaped spacer after the substrate is developed, and the spacer can be arranged in a region other than the R, G, and B pixels, thereby improving scattering incidence. The problem of reduced contrast caused by light on liquid crystal displays. In addition, the thickness of the spacer body prepared by this method is excellent, the two cell gaps are easy to control, and the accuracy is also greatly improved, which is extremely important for a high-resolution liquid crystal display (LCD).

Although the photosensitive resin type spacer can obtain good gap uniformity (for example, JP-A-2006-184841), the liquid crystal molecules are easily squeezed due to insufficient buffer space, causing the liquid crystal display element to have a hue during development. Uneven, poor quality and other issues. In response to this problem, the industry is currently using a weak exposure process with a halftone mask to improve it.

In the weak exposure process of the halftone mask, a gap can be formed between the gap bodies formed, and the halftone mask of different transmittance can adjust the range of the step, so that the liquid crystal molecules can be greatly buffered between the two substrates. space.

However, when a photosensitive resin composition of a conventional spacer is applied to a weak exposure process of a halftone mask, a spacer having a high sensitivity and a sharp profile cannot be obtained.

In view of the above, it is not necessary to provide a photosensitive resin composition, and in order to improve the conventional photosensitive resin composition, when a weak exposure process using a halftone mask is applied, a gap of a high sensitivity and an upright profile cannot be obtained.

Therefore, an aspect of the present invention provides a photosensitive resin composition comprising at least an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), and a photoinitiator ( C) and a carboxylic acid compound (D).

Another aspect of the present invention provides a spacer body which is sequentially pre-baked, exposed, developed, and post-baked by the photosensitive resin composition to form a pattern having high sensitivity and an upright contour. The gap body.

According to still another aspect of the present invention, there is provided a liquid crystal display element comprising the above-mentioned interstitial body, thereby improving a conventional photosensitive resin composition, in which a high-sensitivity and an upright profile cannot be obtained when a weak exposure process using a halftone mask is used Disadvantages such as the gap body.

The photosensitive resin composition of the present invention includes an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), and a carboxylic acid compound (D), which are described below.

In the present invention, (meth)acrylic acid means acrylic acid and/or methacrylic acid, and similarly, (meth)acrylate means acrylate and/or methacrylate; The acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group.

Alkali soluble resin (A)

The alkali-soluble resin (A) of the present invention means a resin which is soluble in an alkaline aqueous solution, for example, a carboxylic acid group-containing resin, a phenol-novolac resin, or the like, preferably an unsaturated carboxylic acid. A copolymer obtained by copolymerizing a monomer (a1), an epoxy group-containing unsaturated monomer (a2), and another unsaturated monomer (a3).

The above unsaturated carboxylic acid monomer (a1) is used in an amount of 100 parts by weight based on the total of the unsaturated carboxylic acid monomer (a1), the epoxy group-containing unsaturated monomer (a2), and the other unsaturated monomer (a3). The amount used is preferably 5 to 50 parts by weight, and specific examples thereof include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; maleic acid, horse Unsaturated dicarboxylic acids (anhydrides) such as phthalic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, etc.; unsaturated polyvalent carboxylic acids (anhydrides) of three or more valences . The above enumerated is preferably (meth)acrylic acid. The above unsaturated monomers may be used singly or in combination of plural kinds.

The above epoxy group-containing unsaturated monomer is used in an amount of 100 parts by weight based on the total of the unsaturated carboxylic acid monomer (a1), the epoxy group-containing unsaturated monomer (a2), and the other unsaturated monomer (a3). The amount of (a2) used is preferably from 10 to 70 parts by weight, and specific examples thereof include: glycidyl acrylate, glycidyl methacrylate, and α-ethyl methacrylate (glycidyl α-ethylacrylate), 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, o-vinyl benzyl O-vinylbenzylglycidylether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. The above list is propylene glycol methacrylate, 6,7-epoxyheptyl methacrylate, o-vinyl benzyl epoxidized propyl ether, m-vinyl benzyl epoxypropyl ether and - Vinylbenzyl epoxypropyl ether is preferred.

The use amount of the other unsaturated monomer (a3) based on the total amount of the unsaturated carboxylic acid monomer (a1), the epoxy group-containing unsaturated monomer (a2), and the other unsaturated monomer (a3) is 100 parts by weight. The amount is preferably from 0 to 70 parts by weight, and specific examples thereof include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, butyl methacrylate, and methacrylic acid. An alkyl methacrylate such as butyl ester; an alkyl acrylate such as methyl acrylate or isopropyl acrylate; cyclohexyl methacrylate or methacrylic acid; a cyclic alkyl methacrylate such as 2-methylcyclohexyl ester, dicyclopentanyl methacrylate, dicyclopentyloxyethyl methacrylate or isobornyl methacrylate; Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentyloxy acrylate, etc. cyclic alkyl acrylate; diethyl maleate (diethyl maleate), diethyl fumarate, itaconic acid An ester of a dicarboxylic acid such as an ethyl ester; a hydroxy alkyl methacrylate such as 2-hydroxy ethyl methacrylate or 2-hydroxypropyl methacrylate; Or styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like. The above enumerated styrene, butyl methacrylate, dicyclopentanyl methacrylate, dicyclopentyloxyethyl acrylate, p-methoxy styrene are preferred, generally one kind or a mixture of plural Kind of use.

The solvent used in the production of the alkali-soluble resin (A) of the present invention is generally ethylene glycol monopropyl ether, diethylene glycol dimethyl ether; Diglyme), tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl ethyl ketone and acetone, Among them, diethylene glycol dimethyl ether and propylene glycol monomethyl ether acetate are preferred, and generally used alone or in combination.

The initiator used in the manufacture of the alkali-soluble resin (A) is generally a radical polymerization initiator such as 2,2'-azobisisobutyronitrile or 2,2'-azobis (2,4). - dimethyl valeronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile ( A peroxy compound such as an azo compound such as 2,2'-azobis-2-methyl butyronitrile or AMBN) or a benzoylperoxide.

The alkali-soluble resin (A) of the present invention can be generally used singly or in combination of plural kinds.

Compound containing ethylenically unsaturated group (B)

The ethylenically unsaturated group-containing compound (B) is a compound having at least one or more ethylenically unsaturated groups, and specific examples thereof include acrylamide, (meth) propylene morpholine, and (meth) acrylate-7. -amino-3,7-dimethyloctyl ester, isobutoxymethyl (meth) acrylamide, isobornyl methacrylate, isobornyl (meth)acrylate, (A) 2-ethylhexyl acrylate, ethyl diethylene glycol (meth) acrylate, trioctyl (meth) acrylamide, diacetone (meth) acrylamide, (methyl) Dimethylaminoethyl acrylate, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl Base (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofuran (meth) acrylate, tetrabromo (meth) acrylate Phenyl ester, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, (meth)acrylic acid -2-tribromophenoxyethyl ester, 2-hydroxy-(meth)acrylic acid B , 2-hydroxy-(meth)acrylic acid propyl ester, vinyl caprolactam, N-vinyl pyrrolidone, phenoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, (methyl) a compound having one ethylenically unsaturated group such as pentabromophenyl acrylate, polyethylene mono(meth)acrylate, propylene mono(meth)acrylate, borneol (meth)acrylate; Diol (meth) acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, tris(2- Hydroxyethyl)isocyanate di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylic acid Ester, 1,6-hexanediol di(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, EO modified bisphenol A di(methyl) Acrylate, PO modified bisphenol A di(meth) acrylate, EO modified hydrogenated bisphenol A di(meth) acrylate, PO modified hydrogenated bisphenol A di(meth) acrylate EO modified bisphenol F di(meth) acrylate, phenol a compound having two ethylenically unsaturated groups such as polyglycidyl ether (meth) acrylate; tris(2-hydroxyethyl) isocyanate tri(meth) acrylate; caprolactone modified three ( Tris(meth)acrylate of 2-hydroxyethyl)isocyanate, trimethylolpropyl tri(meth)acrylate, ethylene oxide (hereinafter referred to as EO) modified tris(meth)acrylic acid trihydroxyl Methyl propyl ester, propylene oxide (hereinafter referred to as PO) modified tris (meth) acrylate trimethylol propyl ester, pentaerythritol tri (meth) acrylate, PO modified glycerol tri (methyl) propionic acid a compound having three ethylenically unsaturated groups such as an ester; pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetraacrylate or the like having four ethylenicity a compound having a saturated group; a compound having 5 ethylenically unsaturated groups such as dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate; dipentaerythritol hexaacrylate (dipentaerythritol) Hexaacrylate; DPHA), dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol A compound having six ethylenically unsaturated groups, such as an alcohol hexa(meth)acrylate or an ethylene oxide (hereinafter referred to as EO) modified dipentaerythritol hexaacrylate.

The ethylenically unsaturated group-containing compound (B) also includes a compound having 7 or more ethylenically unsaturated groups obtained by reacting dipentaerythritol penta (meth) acrylate with a tetracarboxylic dianhydride, such as TO-2323, TO-2324, TO-2325, TO-2326, TO-2327, and TO-2328 (Japan East Asia Synthetic System). Among them, specific examples of the tetracarboxylic dianhydride are: ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl Base-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 , 3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,5,6-cyclohexanetetracarboxylic dianhydride, 3, 3',4,4'-dicyclohexyltetracarboxylic dianhydride, dicycloheptane tetracarboxylic dianhydride, 3,3'-dicyclohexyl-1,1',2,2'-tetracarboxylic acid Anhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, Tetracycline (6‧2‧11,3.02,7) dodecane-4,5,9,10-tetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydrogen Naphthalene-1-succinic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene (1,2- c)-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl )-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-six 5-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-di Ketone, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c] -furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)- Naphthalene [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo 3--3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5 -(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl) 3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2‧2‧2]-oct-7-ene-2,3,5,6-tetracarboxylic acid Anhydride, bicyclo[3‧3·0]-octane-2,4,6,8-tetracarboxylic dianhydride, 3-oxabicyclo[3‧2‧1]-octane-2,4- Aliphatic and alicyclic tetracarboxylic dianhydrides such as diketone-6-spiro-3'-(tetrahydrofuran-2',5'-dione); pyromellitic dianhydride, 3,3',4 , 4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4-diphenyltetracarboxylic dianhydride, 3,3 , 4,4'-biphenylpyrenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6 , 7-naphthalenetetracarboxylic dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,5,6-nonanetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) Ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl) Dimethyldecane dianhydride, bis(3,4-dicarboxyphenyl)diphenylnonane dianhydride, 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis (3,4- Dicarboxyphenyl)pyridine dianhydride, 3,3'-4,4'-diphenylmethanetetracarboxylic dianhydride, 3,3'-4,4'-diphenylethane tetracarboxylic dianhydride, 3,3'-4,4'-diphenylpropane tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'- Dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis(3,4-dicarboxybenzyl)diphenylmethane dianhydride, 4,4'-bis(3,4-dicarboxybenzyl)diphenylethane dianhydride 4,4'-bis(3,4-dicarboxybenzyl)diphenylpropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylmethane dianhydride, 4,4' - bis(3,4-dicarboxyphenoxy)diphenylethane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-double (3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'- Perfluoropropylene dibenzoic dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-diphenyltetracarboxylate Acid dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, bis(phthalic acid) benzene sulphur oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m- Phenyl-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4, 4'-diphenylmethane dianhydride, ethylene glycol-bis(hydroper trimellitate), propylene glycol-bis(hydroper trimellitate), 1,4-butanediol-bis (dehydrated trimellitate) Acid ester), 1,6-hexanediol-bis(hydrogen trimellitate), 1,8-octanediol-bis(hydroper trimellitate), 2,2-bis(4-hydroxybenzene) Propane-bis(dehydrated trimellitic acid) Aromatic tetracarboxylic dianhydrides such as esters.

In the ethylenically unsaturated group-containing compound (B) of the present invention, a compound having three or more ethylenically unsaturated groups is preferred, and more preferably four or more ethylenically unsaturated groups are present. Further, it is more preferably a compound having 5 or more ethylenically unsaturated groups. The above ethylenically unsaturated group-containing compound (B) may be used singly or in combination of plural kinds.

In general, the ethylenically unsaturated group-containing compound (B) of the present invention is used in an amount of usually 5 to 450 parts by weight, preferably 10 to 400 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). More preferably, it is 20 to 300 parts by weight. Among them, the compound having 3 or more ethylenically unsaturated groups is usually used in an amount of 5 to 250 parts by weight, preferably 10 to 230 parts by weight, more preferably 15 to 200 parts by weight.

When the compound having 3 or more ethylenically unsaturated groups is used in an amount of 5 to 250 parts by weight, the erecting of the obtained gap body contour can be further improved in the weak exposure process of the halftone mask. Sex.

Photoinitiator (C)

The photoinitiator (C) of the present invention may comprise a biimidazole compound (C-1) as shown in formula (I) or formula (II):

Wherein X of the formula (I) represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, and A represents -COO- R ₁ and R ₁ represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, m represents an integer of 1 to 3, and n represents an integer of 1 to 3.

Wherein X ₁ , X ₂ and X _{3 of the} formula (II) represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an aromatic group having 6 to 9 carbon atoms. The groups, X ₁ , X ₂ and X ₃ are each the same or different, but the three are not simultaneously a hydrogen atom.

Specific examples of the biimidazole compound (C-1) represented by the above formula (I) are, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-fluorene (4) -2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole], 2,2'-double (2 -Chlorophenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl)diimidazole [2,2'-bis(2-chlorophenyl)-4,4',5,5 '-tetrakis(4-phenoxycarbonylphenyl)biimidazole], 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl) Imidazole [2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole], 2,2'-bis(2,4-dichlorophenyl) -4,4',5,5'-indole (4-phenoxycarbonylphenyl)diimidazole [2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'- Tetrakis(4-phenoxy carbonylphenyl)biimidazole], 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl) 2,2'-bis(2,4,6-trichlorophenyl-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole], 2,2'-bis (2,4,6 -trichlorophenyl)-4,4',5,5'-indole (4-phenoxycarbonyl) Phenyl) 2,2'-bis(2,4,6-trichlorophenyl-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole], 2,2'-bis(2- Cyanophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)diimidazole [2,2'-bis(2-cyanophenyl)-4,4',5,5 '-tetrakis(4-ethoxycarbonylphenyl)biimidazole,], 2,2'-bis(2-cyanophenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl)diimidazole [2,2'-bis(2-cyanophenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole], 2,2'-bis(2-methylphenyl)-4,4 ',5,5'-肆(4-methoxycarbonylphenyl)diimidazole [2,2'-bis(2-methylphenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)biimidazole ,],2,2'-bis(2-methylphenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)diimidazole [2,2'-bis (2 -methylphenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole], 2,2'-bis(2-methylphenyl)-4,4',5,5'-oxime ( 4-Butoxycarbonylphenyl)diimidazole [2,2'-bis(2-methylphenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole], 2,2'-double ( 2-ethylphenyl)-4,4',5,5'-indole (4-methoxy 2,2'-bis(2-ethylphenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)biimidazole], 2,2'-bis(2-ethyl Phenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)diimidazole [2,2'-bis(2-ethylphenyl)-4,4',5,5'- Tetrakis(4-ethoxycarbonylphenyl)biimidazole], 2,2'-bis(2-ethylphenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl)diimidazole [2, 2'-bis(2-ethylphenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole], 2,2'-bis(2-phenylphenyl)-4,4',5 , 5'-(4-methoxycarbonylphenyl) diimidazole [2,2'-bis(2-phenylphenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)biimidazole], 2 , 2'-bis(2-phenylphenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)diimidazole [2,2'-bis(2-phenylphenyl)- 4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole], 2,2'-bis(2-phenylphenyl)-4,4',5,5'-indole (4-phenoxy) 2,2'-bis(2-phenylphenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole] and the like.

Specific examples of the biimidazole compound (C-1) represented by the above formula (II) are, for example, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl. 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-fluorophenyl)-4,4',5 , 2'- 2'-bis(o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methylphenyl) -4,4',5,5'-tetraphenyl-imimidazole [2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'- Bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyl -biimidazole], 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(p-methoxyphenyl)-4, 4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2' -bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 , 5'-tetraphenyl-diimidazole [2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole] 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2,4-dibromophenyl)-4,4 ',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2 '-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2,4-dicyanophenyl)-4,4' , 5,5'-tetraphenyl-diimidazole [2,2'-bis(2,4-dicyanophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis (2, 4,6-Tricyanophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2,4,6-tricyanophenyl)-4,4',5, 5'-tetraphenyl-biimidazole], 2,2'-bis(2,4-dimethylphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis (2 , 4-dimethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2,4,6-trimethylphenyl)-4,4',5,5' -2,2'-bis(2,4,6-trimethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2,4-di Ethylphenyl)-4,4',5,5'-tetraphenyl-diimidazole [2,2'-bis(2,4-diethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole] 2,2'-bis(2,4,6-triethylphenyl)-4,4 , 5,5'-tetraphenyldiimidazole [2,2'-bis(2,4,6-triethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-double ( 2,4'-bis(2,4-diphenylphenyl)-4,4',5,5' -tetraphenyl-biimidazole], 2,2'-bis(2,4,6-triphenylphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2 , 4,6-triphenylphenyl)-4,4',5,5'-tetraphenyl-biimidazole] and the like.

The above diimidazole-based compound (C-1) may be used singly or in combination of plural kinds. The diimidazole compound (C-1) represented by the above formula (I) and formula (II) is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-oxime. (4-ethoxycarbonylphenyl)diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl) Diimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorobenzene) -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl Imidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4,6- Tribromophenyl)-4,4',5,5'-tetraphenyldiimidazole is preferred.

Further, the photoinitiator (C) described above may also include other photoinitiator (C-2), such as an oxime-based compound, an acetophenone-based compound, and the like.

Specific examples of other photoinitiators (C-2) are, for example, ethane ketone, 1-[9-ethyl-6-(2-methylbenzomethyl) 9-hydro-oxazol-3- substituent]- , 1-(9-ethyl-6-(2-methylbezoyl)9H-carbozole-3-yl]-1-(O-acetyl oxime)] (eg under the trade name OXE) -02; manufactured by Ciba Specialty Chemicals), ethyl ketone, 1-[9-ethyl-6-(2-chloro-4-phenylsulfobenzoyl) 9-hydro-oxazol-3- substituent]- , 1-(9-ethyl-6-(2-chloro-4-benzylsulfonylbenzoyl)9H-carbozole-3-yl]-1-(O-acetyl oxime)]( For example, manufactured by Asahi Kasei Co., Ltd., 1-(4-phenyl-thiophenyl)-butane-1,2-dione 2-indole-oxy-benzoic acid ester, 1-(4-phenyl-thio Phenyl)-octane-1,2-dione 2-indole-oxy-benzoate (for example, trade name OXE-01; manufactured by Ciba Specialty Chemicals), 1-(4-phenyl-thiophenyl) - an oxane-1-one oxime-oxy-acetate, a lanthanide compound such as 1-(4-phenyl-thiophenyl)-butan-1-one oxime-oxy-acetate; Acetophenone, α,α'-dimethoxy acetophenone, 2,2'-dimethyl-2-acetophenone, p-methoxyacetophenone, 2-methyl-1 -(4-methylthiophenyl)-2- morpholino-1-propanone [2-methyl-1-(4-meth Ylthiophenyl)-2-morpholino-1-propanone], 2-benzyl-2-N,N-dimethylamine-1-(4- morpholinophenyl)-1-butanone [2-benzyl-2- Acetophenone-based compound such as N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone]; thioxantone, 2,4-diethylthioxanthone, thioxanthone-4- a benzophenone compound such as hydrazine, benzophenone, 4,4'-bis(dimethylamine)benzophenone or 4,4'-bis(diethylamine)benzophenone; (benzil), α -diketone compounds such as acetamidine; acyloin compounds such as benzoin; benzophenone methyl ether and benzophenone ether , acyloin ethers such as benzophenone isopropyl ether; 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide, bis-(2,6-dimethoxybenzoquinone) An acylphosphine oxide compound such as -2,4,4-trimethylbenzylphosphine oxide; an anthracene compound such as hydrazine or 1,4-naphthoquinone; phenylhydrazine methyl chloride ( Halide compound such as phenacyl chloride), tribromomethylphenylhydrazine, tris(trichloromethyl)-s-triazine, etc.; di-tertiary butyl peroxide It Peroxide and the like.

The above other photoinitiators (C-2) may be used singly or in combination of plural kinds. The other photoinitiators (C-2) listed above are ethyl ketone, 1-[9-ethyl-6-(2-methylbenzomethyl) 9-hydro-oxazol-3- substituent] Further, 1-(oxy-acetamidine), 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone or the like is preferred.

Further, the photoinitiator (C) of the present invention is usually used in an amount of 40 to 80 parts by weight, preferably 45 to 75 parts by weight, based on 100 parts by weight of the ethylenically unsaturated group-containing compound (B). It is preferably 50 to 70 parts by weight. Further, the diimidazole-based compound (C-1) is used in an amount of usually 30 to 60 parts by weight, preferably 35 to 55 parts by weight, more preferably 40 to 50, based on 100 parts by weight of the photoinitiator (C). Parts by weight. If the diimidazole compound (C-1) is not used, there is a problem that the sensitivity is low in the weak exposure process of the halftone mask.

Carboxylic acid compound (D)

The carboxylic acid compound (D) of the present invention may comprise a structure as shown in the formula (III):

Wherein R _{2 of the} formula (III) represents a single bond, a saturated linear chain, a saturated branched chain or an unsaturated straight chain.

When R ₂ of the above formula (III) is a single bond, the carboxylic acid compound (D) is specifically, for example, 2-furoic acid or 3-furancarboxylic acid.

When R ₂ of the above formula (III) is a saturated linear chain, specific examples of the carboxylic acid compound (D) are, for example, 2-(2-furyl)acetic acid, 3-(2-furyl)propionic acid, 4-(2- Furyl)butyric acid, 5-(2-furyl)pentanoic acid, 6-(2-furyl)hexanoic acid, 7-(2-furyl)heptanoic acid, 8-(2-furyl)octanoic acid, 9 -(2-furyl) decanoic acid and the like.

When R ₂ of the above formula (III) is a saturated branch, the specific one of the carboxylic acid compound (D) is, for example, 3-(2-furyl)-2-methylpropionic acid or 4-(2-furyl)-2. Ethylpropionic acid, 5-(2-furyl)-3-methylpentanoic acid, 5-(2-furyl)-3,4-dimethylvaleric acid, and the like.

When R ₂ of the above formula (III) is an unsaturated straight chain, specific examples of the carboxylic acid compound (D) include 2-furylacrylic acid and 3-furylacrylic acid.

The above carboxylic acid compound (D) may be used singly or in combination of plural kinds. The above carboxylic acid compound (D) is preferably 2-furancarboxylic acid, 3-furancarboxylic acid, 3-(2-furyl)propionic acid and 3-(2-furyl)-2-methylpropionic acid. .

The above carboxylic acid compound (D) is used in an amount of usually 0.5 to 10 parts by weight; preferably 1 to 8 parts by weight; more preferably 1.5 to 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). If the carboxylic acid compound (D) is not used, in the weak exposure process of the halftone mask, a collapse phenomenon occurs and a gap body having an upright profile cannot be obtained.

It is worth mentioning that the weight ratio of the photoinitiator of the diimidazole compound (C-1) to the carboxylic acid compound (D) of the above formula (III) in the photosensitive resin composition of the present invention (C-1) / (D) is usually from 3 to 35, preferably from 5 to 30, more preferably from 10 to 25. If the weight ratio (C-1)/(D) of the photoinitiator of the diimidazole compound (C-1) to the carboxylic acid compound (D) of the above formula (III) is from 3 to 35, the present invention The photosensitive resin composition can form a gap body of high sensitivity and upright profile in a weak exposure process of a halftone mask.

Solvent (E)

In the present invention, the solvent (E) is capable of dissolving the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C), and the carboxylic acid compound (D), and is not the same as described above. It is preferred that the components react with each other and have appropriate volatility.

Specific examples of the above solvent (E) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and diethylene glycol mono-positive Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol (poly)alkylene glycol monoalkyl ethers such as mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate (poly)alkylene glycol monoalkyl ether acetates such as ester, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethacrylate Other ethers such as diglyme, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone Classes; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, 3 -methyl methoxypropionate, 3-methyl Ethyl propyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate , 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate , isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, Other esters such as ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; N- A carboxylic acid amine such as methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.

The above solvent (E) may be used singly or in combination of plural kinds. The solvent (E) listed above is preferably diethylene glycol dimethyl ether or propylene glycol monoethyl ether acetate.

The solvent (E) is used in an amount of usually 500 to 3,500 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); preferably 800 to 3,200 parts by weight; more preferably 1,000 to 3,000 parts by weight.

Additive (F)

The photosensitive resin composition described above may more preferably include the additive (F), and the additive (F) may include, but is not limited to, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, and the like.

Specific examples of the above additive (F) are: glass, aluminum filler; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2) -aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidylpropyltrimethoxydecane, 3-glycidylpropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3- Chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane (for example, trade name KBM-503; manufactured by Shin-Etsu Chemical Co., Ltd.), 3-sulfur Adhesion aid such as alcohol propyl trimethoxy decane; resistance to 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, etc. Oxidizing agent; ultraviolet absorber such as 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide or alkoxyphenone; and anti-agglomerating agent such as sodium polyacrylate .

In general, the above additive (F) is used in an amount of usually from 0 to 10 parts by weight, preferably from 0 to 6 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), and most preferably from 0 to 3 parts by weight. good.

In addition, the above additive (F) may further include a surfactant, which is specifically, for example, a polyethylene oxide such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether or the like. Ethylene ethers; polyethylene oxide alkyl phenyl ethers such as polyethylene oxide octyl phenyl ether and polyethylene oxide nonyl phenyl ether; polyethylene glycol dilaurate, polyethylene Polyethylene glycol diesters such as alcohol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; the following trade name: KP (Shin-Etsu Chemical Co., Ltd.), SF-8427 (manufactured by Toray Dow Corning Silicone), Polyflow (manufactured by Kyoei Oil & Fats Chemical Industry Co., Ltd.), F-Top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink and Chemical Industry), Fluorade (Sumitomo 3M system), Surflon (Asahi Glass system) and so on. The above surfactants may be used singly or in combination of plural kinds or more.

The surfactant is generally used in an amount of from 0 to 6 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), preferably from 0 to 3 parts by weight. The above surfactant can contribute to the improvement of the coatability of the above-mentioned photosensitive resin composition.

Photosensitive resin composition

The photosensitive resin composition of the present invention generally comprises the above alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a carboxylic acid compound (D), and a solvent (E). The mixture is placed in a stirrer to be stirred, and uniformly mixed into a solution state, and if necessary, additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and a surfactant may be added.

Method for manufacturing spacer body

The spacer of the present invention can be applied to a substrate by a coating method such as spin coating, roll coating or cast coating, and then prebaked. The solvent is removed to form a prebaked coating film. The pre-baking conditions vary depending on the type and blending ratio of each component, and are usually carried out at a temperature of 70 to 90 ° C for 1 to 15 minutes. After pre-baking, the coating film is irradiated with ultraviolet light under a designated halftone mask to perform a weak exposure process. Thereafter, the film was immersed in a developing solution at a temperature of 23 ± 2 ° C for 30 seconds to 5 minutes, and the unnecessary portion was removed to form a pattern. Among them, the light used for the exposure is preferably ultraviolet rays such as g-line, h-line, and i-line, and the ultraviolet device may be a (super) high-mercury lamp and a metal halide lamp.

The substrate may be selected from the group consisting of an alkali-free glass, a soda-lime glass, a tempered glass (Pyrex glass), a quartz glass, or a glass having a transparent conductive film adhered thereon, and a substrate for use in a solid-state imaging device. A photoelectric conversion device substrate (such as a germanium substrate) or the like.

Further, specific examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine, and Basicity of methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-(5,4,0)-7-undecene Compound. The concentration of the developer is generally 0.001 to 10% by weight, preferably 0.005 to 5% by weight, more preferably 0.01 to 1% by weight. When such a developer is used, it is usually washed with water after development. Next, the pattern is air-dried with compressed air or compressed nitrogen, and then post-baked by a heating device such as a hot plate or an oven. The post-baking temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 60 minutes, and the heating time using the oven is from 30 minutes to 90 minutes.

Method for manufacturing liquid crystal display element

The liquid crystal display element of the present invention has a spacer body made of the above-mentioned photosensitive resin composition, and can be produced by the following method (a) or (b).

(a) First, two transparent substrates having a transparent conductive film (electrode) are provided, and a gap body is formed on one of the transparent substrates by the above-mentioned photosensitive resin composition. Next, after forming a liquid crystal alignment film on the transparent conductive film of the transparent substrate and the spacer, the two transparent substrates are opposed to each other (the liquid crystal alignment film faces inward) and an injection hole is left. Finally, a liquid crystal display element can be obtained by injecting a liquid crystal and sealing the injection hole, and then attaching a polarizing plate to the outside of the two transparent substrates.

(b) In another embodiment, after the two transparent substrates of the above method (a) are formed into an alignment film, an ultraviolet curable frame seal is applied to the peripheral edges of one of the transparent substrates. Next, after the liquid crystal was dropped on the transparent substrate in the form of fine droplets, the two transparent substrates were bonded to each other under vacuum, and the frame rubber was hardened and sealed by irradiation with ultraviolet rays. Finally, a polarizing plate is attached to the outside of the two transparent substrates to obtain a liquid crystal display element.

The liquid crystal used in the above, that is, the liquid crystal compound or the liquid crystal composition is not particularly limited herein, and any liquid crystal compound and liquid crystal composition can be used.

Further, the liquid crystal alignment film used as described above is used to restrict the alignment of liquid crystal molecules, and is not particularly limited herein, and any of an inorganic substance or an organic substance may be used. The technique for forming a liquid crystal alignment film is well known to those of ordinary skill in the art to which the present invention pertains, and is not the focus of the present invention, and therefore will not be further described.

The following embodiments are used to illustrate the application of the present invention, and are not intended to limit the present invention. Those skilled in the art can make various changes without departing from the spirit and scope of the present invention. Retouching.

Synthesis Example 1: Method for Producing Alkali Soluble Resin (A-1)

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked flask of 1000 ml volume, and after introducing nitrogen, 30 parts by weight of methacrylic acid (hereinafter referred to as MAA) and glycidyl methacrylate were added. (hereinafter referred to as GMA) 25 parts by weight, 35 parts by weight of butyl methacrylate (hereinafter referred to as TBMA), 10 parts by weight of styrene (hereinafter referred to as SM), 2,2'-azobis-2-methylbutyl Nitrile (hereinafter abbreviated as AMBN) 3.1 parts by weight, and diethylene glycol dimethyl ether solvent 240 parts by weight. The solution was warmed to 85 ° C with slow agitation and polymerized at this temperature for 6 hours. Then, the solvent is devolatilized to obtain an alkali-soluble resin (A-1).

Synthesis Example 2: Method for Producing Alkali Soluble Resin (A-2)

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked flask of 1000 ml volume, and after introducing nitrogen, 15 parts by weight of MAA, 10 parts by weight of acrylic acid (hereinafter referred to as AA), and 25 parts by weight of GMA were added. 30 parts by weight of TBMA, 20 parts by weight of benzyl methacrylate monomer (hereinafter referred to as BzMA), 3.1 parts by weight of AMBN, and 240 parts by weight of diethylene glycol dimethyl ether solvent. The solution was warmed to 85 ° C with slow agitation and polymerized at this temperature for 6 hours. Then, the solvent is devolatilized to obtain an alkali-soluble resin (A-2).

Synthesis Example 3: Method for Producing Alkali Soluble Resin (A-3)

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked flask of 1000 ml volume. After introducing nitrogen, 30 parts by weight of AA, 30 parts by weight of GMA, 25 parts by weight of BzMA, and 15 parts by weight of SM were added. AMBN 3.1 parts by weight, and 240 parts by weight of diethylene glycol dimethyl ether solvent. The solution was warmed to 85 ° C with slow agitation and polymerized at this temperature for 6 hours. Then, the solvent is devolatilized to obtain an alkali-soluble resin (A-3).

Method for producing photosensitive resin composition

The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were prepared according to Table 1 below.

Example 1

100 parts by weight of the alkali-soluble resin (A-1), 75 parts by weight of 2-hydroxy-ethyl methacrylate (B-1), 50 parts by weight of the photoinitiator (C), and 2 parts by weight of 2 The furancarboxylic acid (D-1) was mixed and dissolved in 800 parts by weight of a solvent (E) to prepare a photosensitive resin composition of Example 1. Wherein the above photoinitiator (C) comprises 20 parts by weight of 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole (C) -1-1), 1 part by weight of ketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9hydro-oxazol-3- substituent]-, 1- (oxy-acetonitrile; C-2-1) (trade name: OXE-02; manufactured by Ciba Specialty Chemicals), 29 parts by weight of 2-benzyl-2-N,N-dimethylamine-1-(4- Morpholinophenyl)-1-butanone (C-2-2) (trade name: IRGACURE 907; manufactured by Ciba Specialty Chemicals). The above solvent (E) includes 500 parts by weight of diethylene glycol dimethyl ether (diglyme; E-1) and 500 parts by weight of propylene glycol monomethyl ether acetate (E-2). Thereafter, the sensitivity of the spacer formed by the photosensitive resin composition and the shape of the post-baking pattern are detected, and the method of detecting the sensitivity and the shape of the post-bake pattern will be described later.

Examples 2 to 9

The method for producing the photosensitive resin composition of Example 1 differs in that Examples 2 to 9 change the kind and amount of the raw material in the photosensitive resin composition, and the formulation and test results are shown in Table 1.

Comparative Examples 1 to 4

The method for producing a photosensitive resin composition of the first embodiment differs in that the comparative examples 1 to 4 change the kind and amount of the raw material in the photosensitive resin composition, and the formulation and test results are shown in Table 1.

Compound

B-1 2-hydroxy-ethyl methacrylate

B-2 1,6-hexanediol dimethacrylate

B-3 Trimethylolpropyl acrylate

B-4 pentaerythritol tetraacrylate

B-5 dipentaerythritol hexaacrylate

C-1-1 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole

C-1-2 2,2'-bis(2-chlorophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)diimidazole

C-2-1 ethane ketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9hydro-indazole-3-substituted]-, 1-(oxy-acetonitrile)肟) (trade name OXE-02; manufactured by Ciba Specialty Chemicals)

C-2-2 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone (trade name: IRGACURE 907; manufactured by Ciba Specialty Chemicals)

D-1 2-furancarboxylic acid

D-2 3-(2-furyl)propionic acid

D-3 3-(2-furyl)-2-methylpropionic acid

E-1 diethylene glycol dimethyl ether

E-2 propylene glycol monomethyl ether acetate

E-3 3-ethoxypropionate ethyl ester

F-1 adhesion aid: 3-methacryloxypropyltrimethoxydecane (trade name KBM-503; manufactured by Shin-Etsu Chemical Co., Ltd.)

F-2 surfactant: trade name SF-8427; made by Toray Dow Corning Silicone

Method for manufacturing spacer body

Each of the photosensitive resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 was applied by spin coating on a glass substrate, and prebaked at 90 ° C for 2.5 minutes to obtain a pre-baked portion of about 4 μm. Coating film. Then, the coating film was irradiated with ultraviolet light (exposure model AG500-4N; manufactured by M&R Nano Technology) at 100 mJ/cm ² under a specified halftone mask (transmittance: 50%) to perform a weak exposure process. . Thereafter, the developing solution (2.38% tetramethylammonium hydroxide) immersed in 23 ° C was developed for 2 minutes, and the unexposed portion was removed, and then washed with pure water, and then baked at 235 ° C for 30 minutes to be in the glass. A patterned spacer is formed on the substrate.

Effectiveness evaluation of the gap body

The gap body prepared as described above can be tested for the sensitivity and the shape of the post-bake pattern according to the following steps to evaluate its performance.

1. Sensitivity:

The pre-baked coating film prepared above was placed under the specified halftone mask (transmittance: 50%), and irradiated with ultraviolet light of different exposure amounts (exposure model AG500-4N; manufactured by M&R Nano Technology) to be weak. Exposure process. Thereafter, a film thickness (δ) was measured on the coating film, and then developed by developing the solution (2.38% tetramethylammonium hydroxide) at 23° C. for 2 minutes, and then measured at the same measurement point. Another film thickness (δ _d ). Finally, the residual film ratio can be obtained by the following formula (IV).

Residual film rate (%) = [(δ _d ) / (δ)] × 100 (IV)

The exposure amount when the residual film ratio is 90% or more is called sensitivity, and is evaluated according to the following criteria:

○: Exposure amount ≦110 mJ/cm ²

╳: Exposure amount >110 mJ/cm ²

2. Post-bake pattern shape:

The gap body prepared as described above can be used to observe the cross-sectional shape (ie, contour) of the back-baked pattern of the gap body by using the above-mentioned scanning electron microscope, and a width (D _T ) can be measured at the upper opening, and can be measured at the bottom opening. Another width (D _B ) is obtained, and finally the contour ratio (P) is obtained by the following formula (V), and the evaluation result of the shape of the post-bake pattern is represented by the contour ratio value.

Contour ratio (P) = [(D _T ) / (D _B )] × 100 (V)

◎: contour ratio ≧98%

○: 98%> contour ratio ≧ 96%

△: 96%> contour ratio ≧ 94%

╳: contour ratio <94%

The results of the evaluation of the sensitivity and the shape of the post-bake pattern of the patterned gap body obtained in the foregoing examples are shown in Table 1.

As is apparent from the results of the first table, when the photoinitiator (C-1) and the carboxylic acid compound (D) are added to the photosensitive resin composition, the resulting interstitial body exhibits a better sensitivity and a post-bake pattern shape. Therefore, the object of the present invention can be achieved.

Comparative Example 5

The method for producing the photosensitive resin composition of Example 1 was different in that Comparative Example 5 used citraconic acid instead of 2-furancarboxylic acid (D-1). The performance evaluation was performed by each of the above-mentioned test items, and the obtained sensitivity and the shape of the post-bake pattern were all ╳.

Comparative Example 6

The method for producing the photosensitive resin composition of Example 1 was different in that Comparative Example 6 used 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyl). An ester of phenyl)ethyl]benzene (TPPA) with o-naphthoquinonediazide-5-sulfonic acid (trade name DPAP200, manufactured by DKC, average esterification degree of 67%), substituted for ethylenically unsaturated groups Compound (B) and photoinitiator (C). The performance evaluation was performed by each of the above-mentioned test items, and the obtained sensitivity and the shape of the post-bake pattern were all ╳.

It should be noted that, in the present invention, the photosensitive resin composition, the interstitial body, and the liquid crystal display element including the same according to the specific compound, composition, reaction conditions, process, analysis method or specific instrument are exemplified. It is to be understood by those skilled in the art that the present invention is not limited thereto, and the photosensitive resin composition, the spacer, and the liquid crystal display element including the same according to the present invention are not limited thereto. The compound, composition, reaction conditions, process, analytical method or instrument.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

Claims (10)

A photosensitive resin composition comprising: an alkali-soluble resin (A); a compound (B) containing an ethylenically unsaturated group; and a photoinitiator (C), wherein the photoinitiator (C) comprises a formula (I) Or a diimidazole compound (C-1) represented by the formula (II): Wherein X of the formula (I) represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, and A represents -COO- R ₁ and R ₁ represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, m represents an integer of 1 to 3, and n represents an integer of 1 to 3; Wherein X ₁ , X ₂ and X _{3 of the} formula (II) represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an aromatic group having 6 to 9 carbon atoms. a group, X ₁ , X ₂ and X ₃ are each the same or different, but the three are not simultaneously a hydrogen atom; and the carboxylic acid compound (D), wherein the carboxylic acid compound (D) comprises as shown in the formula (III) structure: Wherein R _{2 of the} formula (III) represents a single bond, a saturated linear chain, a saturated branched chain or an unsaturated straight chain, and the diimidazole-based compound (C-1) and the carboxylic acid compound represented by the formula (III) D) has a weight ratio (C-1) / (D) of 3 to 35. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) is composed of an unsaturated carboxylic acid monomer (a1), an epoxy group-containing unsaturated monomer (a2), and the like. The unsaturated monomer (a3) is obtained by copolymerization. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (B) is a compound having three or more ethylenically unsaturated groups. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (B) is a compound having four or more ethylenically unsaturated groups. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (B) is a compound having five or more ethylenically unsaturated groups. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated group-containing compound (B) is used in an amount of 5 to 450 based on 100 parts by weight of the alkali-soluble resin (A). And the carboxylic acid compound (D) represented by the formula (I) is used in an amount of from 0.5 part by weight to 10 parts by weight. The photosensitive resin composition according to claim 1, wherein the photoinitiator (C) is used in an amount of 40 to 80 based on 100 parts by weight of the ethylenically unsaturated group-containing compound (B). Parts by weight. The photosensitive resin composition according to claim 1, wherein the diimidazole compound (C-1) is used in an amount of 30 to 60 parts by weight based on 100 parts by weight of the photoinitiator (C). . A spacer body which is subjected to a prebaking treatment, an exposure treatment, a development treatment, and a post-baking treatment, in accordance with the photosensitive resin composition according to any one of claims 1 to 8. A patterned gap body is formed. A liquid crystal display element comprising the interstitial body according to claim 9 of the patent application.