TW201638656A - Photosensitive resin composition and application thereof - Google Patents

Abstract

The present invention relates to a photosensitive resin composition and an application thereof. The aforementioned photosensitive resin composition includes an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photo initiator (C), a quinonediazidesulfonic acid ester (D) and a solvent (E). The photosensitive resin composition can be produced to a spacer or a protective film, and the photosensitive resin composition has a higher resolution and less residues.

Description

Photosensitive resin composition and application thereof

The present invention relates to a photosensitive resin composition, a spacer formed therefor, and a protective film, and more particularly to a photosensitive resin composition having good resolution and less residue.

In general, pixels and black matrices printed on the surface of the color filter layer are uneven. Generally, a protective film is formed on the surface of the color filter layer to hide the unevenness, thereby achieving the requirement of planarization.

Secondly, manufacturing an optical element such as a liquid crystal display element or a solid-state imaging device includes a processing procedure having severe conditions, for example, when a wiring electrode layer is formed by a treatment method of soaking an acidic solvent or an alkaline solution or by a sputtering method. The surface of the substrate can cause localized corrosion or high temperatures.

Therefore, in order to prevent damage to the components on the surface of the component, a protective film must be laid on the surface of the component. The protective film must have excellent adhesion to the substrate and must have high transparency, high surface hardness and a smooth surface. The protective film with high heat resistance and light resistance will not cause discoloration, yellowing or whitening deterioration under long-term use. In addition, the protective film also needs to have good water resistance, chemical resistance, solvent resistance, acid resistance and alkali resistance.

On the other hand, in the conventional color liquid crystal display element, The interlayer distance (cell gap) fixed between the two substrates is maintained. The conventional color liquid crystal display element is randomly sprayed on the entire substrate such as polystyrene beads or bead beads, wherein the diameter of the polystyrene beads or the bead beads is The distance between the two substrates. However, this conventional method causes the light of the backlight to be scattered by the beading due to the uneven distribution of the position and density of the bead, further reducing the contrast of the display element. Therefore, the photosensitive composition for the interstitial body developed by the photolithography method has gradually become the mainstream in the industry.

The formation of the spacer is the sensitivity of the spacer The composition is first applied to the substrate, and a mask having a prescribed pattern is placed between the substrate and the exposure source, and a gap body is formed by exposure and development. According to this method, a gap body can be formed at a specified position other than the R, G, and B pixels to solve the problems of the prior art. Among them, the cell gap can also be controlled by the thickness of the coating film formed by the photosensitive component, and the distance between the cell gaps can be easily controlled, and the precision is high.

Since the protective film or gap system is formed in a color filter or On the substrate, the transparency is extremely high. When applied to a liquid crystal display element, a protective film or a spacer having poor transparency causes an insufficient brightness of the liquid crystal display element to affect the display quality of the liquid crystal display element.

In order to improve the transparency of the protective film or the gap body, the Japanese patent Japanese Patent Publication No. 2010-054561 discloses a photosensitive resin composition for a protective film comprising an alkali-soluble binder resin, a compound of an ethylenically unsaturated group, a photoinitiator and a solvent, wherein the ethylenically unsaturated group is a compound The bonding equivalent of the unsaturated bond is from 90 g/ep to 450 g/eq, and the ethylenically unsaturated group The single compound in the compound has 2 to 4 unsaturated double bonds, and the alkali-soluble binder resin has a weight average molecular weight of 10,000 to 20,000.

Secondly, Japanese Patent Laid-Open No. 2004-240241 discloses A photosensitive resin composition comprising a copolymer, a polymer having an ethylenic unsaturated group, and a photoinitiator, wherein the copolymer is an ethylenically unsaturated carboxylic acid (anhydride), having a ring A compound obtained by copolymerizing a compound of an ethylenic unsaturated group of an oxy group and another ethylenically unsaturated group, and the photoinitiator may be 2-butanedione-[4-methylthiobenzene]-2 -(O-肟acetate), 1,2-butanedione-1-(4-morpholinylphenyl)-2-(O-benzamide), 1,2-octanedione-1- [4-Benzylbenzene]-2-[O-(4-methylbenzhydrazinium) oxime] or an analog thereof. However, this photosensitive resin composition can produce a highly transparent protective film or a spacer, but has a disadvantage of having a low resolution and a large amount of residue.

In view of this, there is an urgent need to develop a high resolution and residual A photosensitive resin composition having a small amount of slag or a protective film is used to overcome the above problems of the conventional protective film or the spacer.

Therefore, an aspect of the present invention provides a photosensitive resin composition comprising an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), and a photoinitiator (C). ), o-naphthoquinone diazide sulfonate (D) and solvent (E), and the photosensitive resin composition has good resolution and less residue.

Another aspect of the present invention provides a spacer or a protective film which is formed by using the above-mentioned photosensitive resin composition.

Still another aspect of the present invention provides a liquid crystal display element comprising the aforementioned spacer or protective film.

According to the above aspect of the invention, a photosensitive resin composition is proposed. The photosensitive resin composition contains an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), an o-naphthoquinonediazide sulfonate (D), and a solvent (E). ), the following analysis.

Alkali soluble resin (A)

The alkali-soluble resin (A) of the present invention means a resin which is soluble in an aqueous alkaline solution, and the structure thereof is not particularly limited. Preferably, the alkali-soluble resin (A) may be a resin having a carboxylic acid group or a phenol-novolac resin or the like. More preferably, the alkali-soluble resin (A) can be obtained by copolymerization of a mixture in the presence of a suitable polymerization initiator.

The mixture may comprise an unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1), an epoxy group-containing unsaturated compound (a2) and/or other unsaturated compound (a3).

Unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1)

The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) may be a compound containing a carboxylic acid group or a carboxylic acid anhydride structure, and an unsaturated bond for polymerizing the bond. The structure of the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) is not particularly limited, and the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) may include, but is not limited to, an unsaturated monocarboxylic acid compound, and is unsaturated. a dicarboxylic acid compound, an unsaturated acid anhydride compound, a polycyclic unsaturated carboxylic acid compound, a polycyclic unsaturated dicarboxylic acid compound or a polycyclic unsaturated acid anhydride compound.

Specific examples of the aforementioned unsaturated monocarboxylic acid compound may include, but are not limited to, (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-(methyl)acrylic acid ethoxylated butyl Acid ester [2-(meth)acryloyloxyethyl succinate monoester], 2-(meth)acryloyl ethoxyethoxy hexahydrophthalate, 2-(methyl) propylene ethoxylate or omega a carboxypolycaprolactone polyol monoacrylate (which may be a product manufactured by East Asia Synthetic Co., Ltd., model number ARONIX M-5300) or the like.

Specific examples of the aforementioned unsaturated dicarboxylic acid compound may include, but are not limited to, maleic acid, fumaric acid, methyl fumaric acid, itaconic acid or citraconic acid, and the like.

The aforementioned unsaturated acid anhydride compound may be an acid anhydride compound of the unsaturated dicarboxylic acid compound.

Specific examples of the polycyclic unsaturated carboxylic acid compound may include, but are not limited to, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2- Alkene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene or 5-carboxy-6-ethyl Bicyclo [2.2.1] hept-2-ene.

Specific examples of the above polycyclic unsaturated dicarboxylic acid compound may include, but are not limited to, 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene.

The polycyclic unsaturated acid anhydride compound may be an acid anhydride compound of the polycyclic unsaturated dicarboxylic acid compound.

The above unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) may be used singly or in combination of plural kinds.

Preferably, the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound Specific examples of (a1) may be acrylic acid, methacrylic acid, maleic anhydride, 2-methylpropenyl ethoxy succinate or 2-methylpropenyl ethoxy hexahydrophthalic acid.

Based on an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a1), And the total amount of the epoxy group-containing unsaturated compound (a2) and the other unsaturated compound (a3) to be described later is 100 parts by weight, and the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) may be used in an amount of 5 parts by weight. The parts by weight to 50 parts by weight, preferably 5 parts by weight to 35 parts by weight, and more preferably 15 parts by weight to 35 parts by weight.

An epoxy group-containing unsaturated compound (a2)

The epoxy group-containing unsaturated compound (a2) may include a (meth) acrylate compound having an epoxy group, an α-alkyl acrylate compound having an epoxy group, or a glycidyl ether compound.

Specifically, the epoxy group-containing (meth) acrylate compound may include, but is not limited to, glycidyl (meth) acrylate, 2-methyl propyl propyl (meth) acrylate, and (meth) acrylate 3 , 4-epoxybutyl acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate or 3,4-epoxycyclohexyl (meth)acrylate Methyl ester, etc.

Specific examples of the above-mentioned epoxy group-containing α-alkyl acrylate compound may include, but are not limited to, α-ethyl acrylate propyl acrylate, α-n-propyl propylene acrylate, and α-n-butyl acrylate epoxy. Propyl ester or α-ethyl acrylate 6,7-epoxyheptyl ester and the like.

Specific examples of the aforementioned glycidyl ether compound may include, but are not limited to, o-vinylbenzyl glycidyl ether (o-vinylbenzylglycidylether), m-vinylbenzylglycidylether or p-vinylbenzylglycidylether.

The above epoxy group-containing unsaturated compound (a2) may be used singly or in combination of plural kinds.

Preferably, the specific example of the epoxy group-containing unsaturated compound (a2) may be glycidyl methacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, or methacrylic acid 6, 7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl ether.

Based on the above-mentioned unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) and the epoxy group-containing unsaturated compound (a2), and other unsaturated compound (a3), the total amount used is 100 parts by weight, and has an epoxy group. The unsaturated compound (a2) may be used in an amount of 5 parts by weight to 30 parts by weight, preferably 5 parts by weight to 20 parts by weight, and more preferably 10 parts by weight to 20 parts by weight.

Other unsaturated compounds (a3)

The other unsaturated compound (a3) may be an alkyl (meth)acrylate, an alicyclic (meth)acrylate, an aryl (meth)acrylate, an unsaturated dicarboxylic acid diester, (methyl) a hydroxyalkyl acrylate, a polyether of (meth) acrylate, an aromatic vinyl compound, or other unsaturated compound other than the foregoing compounds.

Specific examples of the aforementioned alkyl (meth)acrylate may include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth) acrylate, (a Base) isobutyl acrylate, secondary butyl (meth) acrylate or tertiary butyl (meth) acrylate.

Specific examples of the aforementioned (meth)acrylic alicyclic ester may include, but are not limited to, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and tricyclo [5.2.1.0 ^2,6癸-8-yl (meth) acrylate [may also be referred to as dicyclopentyl (meth) acrylate], dicyclopentyloxy (meth) acrylate, isobornyl (meth) acrylate or Tetrahydrofuranyl (meth)acrylate or the like.

Specific examples of the aryl (meth)acrylate may include, but are not limited to, phenyl (meth)acrylate or benzyl methacrylate.

Specific examples of the unsaturated dicarboxylic acid diester may include, but are not limited to, diethyl maleate, diethyl fumarate or diethyl itaconate.

Specific examples of the aforementioned hydroxyalkyl (meth)acrylate may include, but are not limited to, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

Specific examples of the polyether of the (meth) acrylate may include, but are not limited to, polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate.

Specific examples of the above aromatic vinyl compound may include, but are not limited to, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene or p-methoxystyrene.

Specific examples of the unsaturated compound other than the above compound may include, but are not limited to, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3- Butadiene, isoprene, 2,3-dimethyl1,3-butadiene, N-cyclohexylmaleimide, N-benzene Kimalyimide, N-benzylmaleimide, N-butylenediamine-3-maleimide benzoate, N-butanediamine-4-mer醯iminobutyrate, N-butanediamine-6-maleimide caproate, N-butylenediamine-3-maleimide propionate or N- (9-Acridine) Maleimide and the like.

The other unsaturated compound may be used alone or in combination of plural kinds.

Specific examples of the other unsaturated compound (a3) may preferably be methyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, or tertiary (meth)acrylate. Ester, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, styrene or p-methoxystyrene.

Based on the aforementioned unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) and the epoxy group-containing unsaturated compound (a2), and the other unsaturated compound (a3) are used in an amount of 100 parts by weight, other unsaturated compounds The amount of (a3) used may be from 20 parts by weight to 90 parts by weight, preferably from 45 parts by weight to 90 parts by weight, and more preferably from 45 parts by weight to 75 parts by weight.

The solvent used in the production of the alkali-soluble resin (A) of the present invention may be an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate acetate, a diethylene glycol, a dipropylene glycol, or a propylene glycol monoalkyl group. Ether, propylene glycol alkyl ether acetate acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbons, ketones or esters, and the like.

Specific examples of the alcohol solvent may include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol or 3-phenyl-1-propanol.

Specific examples of the ether solvent may include tetrahydrofuran or the like.

Specific examples of the aforementioned glycol ether may include ethylene glycol monopropyl ether, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether.

Specific examples of the ethylene glycol alkyl ether acetate may include ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate or ethylene glycol methyl ether acetate.

Specific examples of the diethylene glycol may include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or diethyl Glycol methyl ether and the like.

Specific examples of the dipropylene glycol may include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether or dipropylene glycol methyl ethyl ether.

Specific examples of the propylene glycol monoalkyl ether may include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether.

Specific examples of the propylene glycol alkyl ether acetate may include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, or propylene glycol butyl ether acetate.

Specific examples of the propylene glycol alkyl ether propionate may include propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate or propylene glycol butyl ether propionate.

Specific examples of the above aromatic hydrocarbons may include toluene or xylene.

Specific examples of the ketones may include methyl ethyl ketone, cyclohexanone or diacetone alcohol.

Specific examples of the above esters may include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2. -ethyl methacrylate, methyl glycolate, hydroxyethyl Ethyl acetate, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionic acid Butyl ester, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate , propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, Ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 3-methoxybutyl acetate, methyl 2-methoxypropionate, and 2-methoxypropionic acid Ester, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropionate Ester, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionic acid Ester, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid , 3-methoxypropionic acid butyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate , methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate Ethyl 3-butoxypropionate, propyl 3-butoxypropionate or butyl 3-butoxypropionate.

The solvent may be used alone or in combination of plural kinds.

Preferably, a specific example of the solvent may be diethylene glycol dimethyl ether or propylene glycol methyl ether acetate.

Specific examples of the polymerization initiator may be an azo compound, a peroxide or the like.

Specific examples of the azo compound may include, but are not limited to, 2, 2'- Azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylpentyl) Nitrile), 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid) or 2,2'-azobis(dimethyl- 2-methylpropionate) and the like.

Specific examples of the peroxide may include, but are not limited to, peroxide 2 Benzoquinone, dilauroyl peroxide, tert-butyl peroxypivalate, 1,1-di(t-butylperoxy)cyclohexane [1, 1-di(tert-butylperoxy)cyclohexane] or hydrogen peroxide.

The polymerization initiator may be used alone or in combination of plural kinds. use.

Compound having ethylenically unsaturated group (B)

The compound (B) having an ethylenically unsaturated group in the present invention may include the first compound (B-1) having a structure represented by the following formula (II) and another compound (B-2) having an ethylenically unsaturated group.

First compound (B-1) having a structure represented by formula (II)

The aforementioned first compound (B-1) may have a structure represented by the following formula (II):

In the formula (II), R ₃ each independently represents a hydrogen atom or a methyl group. R ₄ each independently represents a hydrogen atom, an acryloyl group or a methacryl group. n represents an integer from 2 to 4.

The first compound having a structure as shown in formula (II) Specific examples of (B-1) may include, but are not limited to, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol pentoxide (meth) acrylate, and pentaerythritol decene (methyl) Acrylate, pentaerythritol eleven (meth) acrylate, pentaerythritol dodeca (meth) acrylate or any combination of the above.

The total amount used based on the alkali-soluble resin (A) is 100% by weight. The first compound (B-1) having a structure represented by the formula (II) is used in an amount of 30 parts by weight to 300 parts by weight, preferably 40 parts by weight to 250 parts by weight, and more preferably 50 parts by weight. Parts by weight to 200 parts by weight.

When the present invention has an ethylenically unsaturated group (B) package When the first compound (B-1) having a structure represented by the formula (II) is contained, the photosensitive resin composition obtained can have a better resolution.

Other compounds having an ethylenically unsaturated group (B-2)

The other ethylenically unsaturated group-containing compound (B-2) may contain a compound having one ethylenically unsaturated group or a compound having at least two ethylenically unsaturated groups.

Specific examples of the compound having one ethylenically unsaturated group may include, but are not limited to, (meth)acrylamide, (meth)acryloylmorpholine, (meth)acrylic acid-7-amine Base-3,7-dimethyloctyl ester, isobutoxymethyl (meth) acrylamide, isobornyloxy (meth)acrylate Ester, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl diethylene glycol (meth) acrylate, third octyl (meth) acrylamide, two Acetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, dodecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (methyl) Dicyclopentyl acrylate, nitrogen, nitrogen-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, ( Tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, (meth)acrylic acid-2- Trichlorophenoxyethyl ester, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, ethyl 2-hydroxy-(meth)acrylate, 2-hydroxy- Propyl (meth)acrylate, vinyl caprolactam, nitrogen-vinylpyrrolidone, phenoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromobenzene (meth)acrylate Ester, poly (mono) (meth) acrylate, poly (mono) (meth) acrylate Or (meth) acrylate, isobornyl acrylate and the like.

The compound having one ethylenically unsaturated group may be used singly or in combination of plural kinds.

Specific examples of the aforementioned compound having at least two ethylenically unsaturated groups may include, but are not limited to, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, and triethylene glycol di(a) Acrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate Acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, tris(meth)acrylic acid trimethylolpropyl ester, ethylene oxide ;hereinafter referred to as EO) modified trimethylolpropyl tris(meth)acrylate, propylene oxide (hereinafter referred to as PO) modified trimethylolpropyl tris(meth)acrylate, tripropylene glycol di Methyl) acrylate, neopentyl glycol di(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, pentaerythritol III (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, Di(trimethylolpropane)tetra(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A II Acrylate, EO modified hydrogenated bisphenol A di(meth)acrylate, PO modified hydrogenated bisphenol A di(meth)acrylate, PO modified tris(meth)propyl Esters, EO-modified bisphenol F di (meth) acrylate or novolak polyglycidyl ether (meth) acrylate.

The compound having at least two ethylenically unsaturated groups may be used singly or in combination of plural kinds.

The compound (B) having an ethylenically unsaturated group is used in an amount of 30 parts by weight to 350 parts by weight, preferably 40 parts by weight to 300 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). Parts, and more preferably 50 parts by weight to 250 parts by weight.

Photoinitiator (C)

The photoinitiator (C) of the present invention is not particularly limited. The light starts The agent (C) may include an O-fluorenyl quinone photoinitiator, a triazabenzene photoinitiator, an acetophenone compound, a diimidazole compound, a benzophenone compound, and an α-diketone. a compound, a keto alcohol compound, a keto alcohol ether compound, a phosphonium oxide compound, an anthraquinone compound, a halogen-containing compound, or a peroxide.

Specific examples of the aforementioned O-fluorenyl quinone photoinitiator may include Not limited to 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-phenylhydrazinyl), 1-[4-(phenylthio)phenyl ]-octane-1,2-dione 2-(O-phenylhydrazinium), 1-[4-(phenylhydrazino)phenyl]-heptane-1,2-dione 2-(O- Phenylhydrazine 肟), ethane ketone-1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-carbazole-3-substituted]-1-(O-ethyl fluorenyl) Ethyl ketone-1-[9-ethyl-6-(3-methylphenylindenyl)-9H-indazole-3-substituted]-1-(O-acetylindenyl), ethane Keto-1-[9-ethyl-6-phenylhydrazin-9H-indazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl- 6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-indazole-3-substituted]-1-(O-acetamidoxime), ethane ketone-1-[9-ethyl -6-(2-methyl-4-tetrahydropyranylphenyl)]-9H-indazole-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[ 9-Ethyl-6-(2-methyl-5-tetrahydrofuranylphenyl)-9H-indazole-3-substituted]-1-(O-ethylindenyl), ethane ketone-1- [9-Ethyl-6-(2-methyl-5-tetrahydropyranylphenyl)]-9H-indazole-3-substituted]-1-(O-ethylindenyl), ethane Keto-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)-9H-indazole-3-substituted]-1-(O-ethylindenyl) ), ethane Keto-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenyl)-9H-indazole-3-substituted]-1-(O-B Ethyl ketone 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxyphenyl)-9H-indazole-3-substituted]-1-(O-ethylindenyl) Ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxyphenyl)-9H-indazole-3-substituted]-1-( O-acetyl hydrazine), ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) Phenylhydrazinyl}-9H-carbazole-3-substituted]-1-(O-acetamidopurine) or eththone-1-[9-ethyl-6-{2-methyl-4-( 2,2-Dimethyl-1,3-dioxolanyl)methoxybenzoquinone}-9H-indazole-3-substituted]-1-(O-ethylindenyl) and the like. The O-fluorenyl fluorene photoinitiator may be used singly or in combination of plural kinds.

Preferably, the specific example of the O-fluorenyl quinone photoinitiator can be 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylhydrazinyl), ethane ketone-1-[9-ethyl-6-( 2-methylphenylhydrazino)-9H-carbazole-3-substituent]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl -4-tetrahydrofuranmethoxyphenyl hydrazino)-9H-carbazole-3-substituted]-1-(O-acetamidoxime) or ethane ketone-1-[9-ethyl-6-{2 -methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxyphenylhydrazinyl}-9H-indazole-3-substituted]-1-(O-乙醯基肟) and so on.

Specific examples of the aforementioned triazabenzene photoinitiator may include but not Restricted to vinyl-halomethyl-s-triazabenzene compounds, 2-(naphtho-1-substituted)-4,6-bis-halomethyl-s-triazabenzene compounds or 4- (p-Aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound.

Specific of the vinyl-halomethyl-s-triazabenzene compound Examples may include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, 2,4-bis(trichloromethyl)-3-(1- p-Dimethylaminophenyl-1,3-butyl Dienyl)-s-triazabenzene or 2-trichloromethyl-3-amino-6-p-methoxystyryl-s-triazabenzene and the like.

The 2-(naphtho-1-substituted)-4,6-bis-halomethyl-s-three Specific examples of the azabenzene compound may include 2-(naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4-methoxy-naphtho -1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis-three Chloromethyl-s-triazabenzene, 2-(4-butoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-[ 4-(2-methoxyethyl)-naphtho-1-substituted]-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-ethoxyl) Ethyl)-naphtho-1-substituted]-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-butoxyethyl)-naphtho-1 -Substituent]-4,6-bis-trichloromethyl-s-triazabenzene, 2-(2-methoxy-naphthyl-1-substituted)-4,6-bis-trichloromethyl Base-s-triazabenzene, 2-(6-methoxy-5-methyl-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(6-methoxy-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(5-methoxy-naphtho-1- Substituent)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4,7-dimethoxy-naphtho-1-substituted)-4,6-bis-three Chloromethyl-s-triazabenzene, 2-(6-ethoxy-naphtho-2-substituted)-4,6-bis-trichloromethyl -s- triazine or 2- (4,5-Dimethoxy - -1- substituent naphtho) -4,6-bis - trichloromethyl -s- triazine and the like.

The 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazole Specific examples of the heterobenzene compound may include 4-[p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene. 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethane) -s-triazabenzene, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p- N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-ethoxycarbonylmethylaminophenyl)-2 ,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-di(phenyl)aminophenyl]-2,6-di(trichloromethyl)- S-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N- (p-methoxyphenyl)carbonylaminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m-N,N-di(ethoxycarbonyl) Methyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo-p-N,N-di(ethoxycarbonylmethyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminobenzene -2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]- 2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-di(ethoxy) Carbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-di(ethoxycarbonylmethyl) Aminophenyl-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-di(ethoxycarbonylmethyl)aminobenzene -2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6 -bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethane) -s-triazabenzene, 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-three Azabenzene, 4-[m-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4- [inter-chloro-pair -N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-di (chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethylaminobenzene) -2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di (trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s -Triazabenzene, 4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4- (o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N -ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-chloroethylaminophenyl) -2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethane) -s-triazabenzene, 4-(m-fluoro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4 -(o-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloromethane) )-s-triazabenzene, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4- (o-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene or 2,4-bis(trichloromethyl)-6 -{3-Bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl}-1,3,5-triazabenzene and the like.

The triazabenzene photoinitiator can be used alone or in combination A variety of uses.

Preferably, the triazabenzene photoinitiator can be 4-[m-bromo- p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethane) Base)-s-triazabenzene or 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene and the like.

Specific examples of the aforementioned acetophenone compound may include, but are not limited to To p-dimethylaminophenone, α,α'-dimethoxyoxyazopropenone, 2,2'-dimethyl-2-phenylacetophenone, p-methoxy Phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-1-propanone or 2-benzyl-2-N,N-dimethylamine- 1-(4-morpholinophenyl)-1-butanone and the like. The acetophenone compounds may be used singly or in combination of plural kinds.

Preferably, the acetophenone compound may comprise 2-methyl 1-[4-(methylthio)phenyl]-2-morpholine-1-propanone or 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinobenzene Base)-1-butanone.

Specific examples of the aforementioned diimidazole compound may include, but are not limited to 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl)-4,4',5 , 5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o- Methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl Diimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,2',4, 4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' - Tetraphenyldiimidazole or 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole or the like. The diimidazole compound may be used singly or in combination of plural kinds.

Preferably, the diimidazole compound may comprise 2,2'-double (2,4-Dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.

Specific examples of the aforementioned benzophenone compound may include, but are not limited to, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-oxime, benzophenone, 4,4'-bis ( Dimethylamine) benzophenone or 4,4'-bis(diethylamine) benzophenone. The benzophenone compound may be used singly or in combination of plural kinds.

Preferably, the benzophenone compound may comprise 4,4'-bis(diethylamine)benzophenone.

Specific examples of the aforementioned α-diketone compound may include, but are not limited to, benzoin or ethenyl.

Specific examples of the ketol compound may include, but are not limited to, benzoin or the like.

Specific examples of the ketol ether compound may include, but are not limited to, benzhydrin methyl ether, benzophenone ethyl ether or diphenylethanol ketone isopropyl ether.

Specific examples of the above phosphonium oxide compound may include, but are not limited to, 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide or bis-(2,6-dimethoxybenzoquinone)-2. 4,4-trimethylphenylphosphine oxide and the like.

Specific examples of the aforementioned quinone compound may include, but are not limited to, hydrazine or 1,4-naphthoquinone or the like.

Specific examples of the halogen-containing compound may include, but are not limited to, benzoquinone methyl chloride, tribromomethylphenylhydrazine or tris(trichloromethyl)-s-triazabenzene.

Specific examples of the aforementioned peroxide may include, but are not limited to, di-tert-butyl peroxide.

The aforementioned photoinitiator (C) may be used singly or in combination of plural kinds.

The total amount used based on the alkali-soluble resin (A) is 100% by weight. The photoinitiator (C) is used in an amount of 15 parts by weight to 100 parts by weight, preferably 17 parts by weight to 90 parts by weight, and more preferably 20 parts by weight to 80 parts by weight.

O-naphthoquinonediazide sulfonate (D)

The o-naphthoquinonediazide sulfonate (D) of the present invention may comprise o-naphthoquinonediazide sulfonate (D-1) having the structure represented by the following formula (I). Secondly, the o-naphthoquinonediazide sulfonate (D) may optionally comprise other o-naphthoquinonediazide sulfonate (D-2):

O-naphthoquinonediazide sulfonate (D-1)

The o-naphthoquinonediazide sulfonate (D-1) has a structure represented by the following formula (I):

In the formula (I), R ₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aromatic group or an alkenyl group. R ₂ each independently represents a hydrogen atom or a functional group having a quinonediazide structure. a, b, d, and e represent integers greater than or equal to 0, respectively, and the sum of f and g is an integer greater than or equal to one. When the sum of a, b, d and e is greater than 1, the plurality of R ₁ may be the same or different respectively; when the sum of f and g is greater than 1, at least one of the plurality of R ₂ has a quinonediazide structure. Functional group.

O-naphthoquinonediazidesulfonic acid having the structure shown in formula (I) The ester (D-1) can be synthesized by using a hydrazine compound having a hydroxyl group, or by reacting an anthrone with phenol, catechol or pyrogallol in the presence of thioacetic acid and an acid contact coal.

O-naphthoquinonediazidesulfonic acid having the structure shown in formula (I) The ester (D-1) is an esterified product which may be fully esterified or partially esterified, preferably obtained by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydrazine compound having a hydroxyl group, more preferably It is prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydrazine compound having a polyhydric hydroxyl group.

Specific examples of the oxime compound having a hydroxyl group may include a product manufactured by JFE Chemical Co., Ltd., and its model is BPF [shown in the following formula (I-1)] or BCF [shown in the following formula (I-2)]; A product manufactured by Chemical Co., Ltd., and its model is BisP-FL [shown by the following formula (I-1)]; or a compound represented by the following formula (I-3) to formula (I-5):

The o-naphthoquinonediazidesulfonic acid may include, but is not limited to, o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid or o-naphthoquinonediazide-6-sulfonic acid, etc. . The salt of the o-naphthoquinonediazidesulfonic acid may include, but is not limited to, an o-naphthoquinonediazidesulfonic acid halide salt, and specific examples may include an o-naphthoquinone diazide-4-sulfonic acid chloride or an o-naphthoquinone Nitrogen-5-sulfonic acid chloride.

The amount of the o-naphthoquinone diazide sulfonate (D-1) to be used is not particularly limited, and the total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the structure has the structure shown in the formula (I). The o-naphthoquinonediazide sulfonate (D-1) is used in an amount of from 1 part by weight to 15 parts by weight, preferably from 1.5 parts by weight to 13 parts by weight, and more preferably from 2 parts by weight to 10 parts by weight.

Further, when the o-naphthoquinonediazide sulfonate (D) of the present invention does not contain o-naphthoquinonediazide sulfonate (D-1) having a structure represented by the formula (I), The photosensitive resin composition has poor resolution and has many residues.

When the o-naphthoquinonediazide sulfonate (D-1) of the structure represented by the formula (I) is used in an amount of from 1 part by weight to 15 parts by weight, the photosensitive resin composition obtained is obtained. The resolution is the best and the residue is the least.

Other o-naphthoquinonediazide sulfonate (D-2)

The o-naphthoquinonediazide sulfonate (D) may optionally have other o-naphthoquinonediazide sulfonate (D-2).

In one embodiment of the invention, the o-naphthoquinonediazide sulfonate (D-2) is an esterified ester which may be fully esterified or partially esterified. The o-naphthoquinonediazide sulfonate (D-2) is preferably derived from o-naphthoquinonediazidesulfonic acid or a salt thereof The hydroxy compound is obtained by a reaction, and more preferably is prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a polyvalent hydroxy compound.

The o-naphthoquinonediazide sulfonic acid may include, but is not limited to, o-naphthoquinone Azide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid or o-naphthoquinonediazide-6-sulfonic acid, and the like. The salt of o-naphthoquinonediazidesulfonic acid may include, but is not limited to, an o-naphthoquinonediazidesulfonic acid halide salt.

The hydroxy compound may include, but is not limited to, hydroxybenzophenones a compound, a hydroxyaryl compound, a (hydroxyphenyl) hydrocarbon compound or other aromatic hydroxy compound. The hydroxy compound may be used singly or in combination of plural kinds.

The aforementioned hydroxybenzophenone compound may include, but is not limited to 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4,4'-four Hydroxybenzophenone, 2,4,2',4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3,4,2' , 4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,5,3',5'-pentahydroxybenzophenone or 2 , 3, 4, 3', 4', 5'-hexahydroxybenzophenone and the like.

The aforementioned hydroxyaryl compound may have a structure represented by the following formula (III-1):

In the formula (III-1), Z ₁ to Z ₃ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and Z ₄ to Z ₉ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, An alkoxy having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a cycloalkyl group; Z ₁₀ and Z ₁₁ representing a hydrogen atom, a halogen atom and a carbon number An alkyl group of 1 to 6; j, k and m represent an integer of 1 to 3; h represents 0 or 1.

The hydroxyaryl compound represented by the formula (III-1) may contain But not limited to tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethyl Phenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl) )-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethyl Phenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl) 3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, Bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3-hydroxyphenyl Methane, bis(3-cyclohexyl-4-hydroxyl -6-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis(3-ring Hexyl-6-hydroxyphenyl)-3-hydroxy Phenyl phenyl methane, bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxyphenylmethane, bis (3) -cyclohexyl-6-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, double (3-cyclohexyl-6-hydroxy-4-methylphenyl)-3,4-dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1, 1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl) -4-hydroxyphenyl)ethyl]benzene or 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol Wait.

The aforementioned (hydroxyphenyl) hydrocarbon compound may have a structure represented by the following formula (III-2):

In the formula (III-2), Z ₁₂ and Z ₁₃ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and p and q represent an integer of 1 to 3.

The (hydroxyphenyl) hydrocarbon compound represented by the formula (III-2) may include, but is not limited to, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'- Trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4) '-Hydroxyphenyl)propane, bis(2,3,4-trihydroxyphenyl)methane or bis(2,4-dihydroxyphenyl)methane.

The other aromatic hydroxy compounds described above may include, but are not limited to, phenol, p-methoxyphenol, dimethyl phenol, hydroquinone, bisphenol A, naphthol, catechol, 1,2,3- Pyrogallol methyl ether, 1,2,3-benzenetriol-1,3- Dimethyl ether, 3,4,5-trihydroxybenzoic acid, or partially esterified or partially etherified 3,4,5-trihydroxybenzoic acid, and the like.

The above hydroxy compound is preferably selected from 1-[1-(4-hydroxyl) Phenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 2,3,4-trihydroxybenzophenone, 2,3,4,4'- Tetrahydroxybenzophenone or any combination of the above.

The o-naphthoquinonediazidesulfonic acid or a salt thereof and a hydroxy compound The reaction is usually carried out in an organic solvent such as dioxane, N-pyrrolidone or acetamide. More preferably, the above reaction is carried out by adding an alkali condensing agent such as triethanolamine, an alkali metal carbonate or an alkali metal hydrogencarbonate.

The degree of esterification of the o-naphthoquinone diazide sulfonate (D) is preferably 50% or more, that is, the total amount of hydroxyl groups in the hydroxy compound is 100 mole percent, and the hydroxyl group has more than 50 mole percent of the hydroxyl group esterified with o-naphthoquinonediazidesulfonic acid or a salt thereof reaction. The degree of esterification of the o-naphthoquinonediazide sulfonate (D) is more preferably 60% or more.

The total amount of the alkali-soluble resin (A) used is 100 The o-naphthoquinonediazide sulfonate (D) may be used in an amount of 1 part by weight to 16 parts by weight, preferably 1.5 parts by weight to 14 parts by weight, and more preferably 2 parts by weight to 12 parts by weight. Share.

Solvent (E)

The solvent (E) of the present invention is completely soluble in other organic components, and its volatility must be high enough to require only a small amount of heat at normal pressure. Evaporation in the dispersion is preferred. Therefore, a solvent having a boiling point of less than 150 ° C at normal pressure is most often used.

The solvent (E) to which the present invention is applicable may include an aromatic solvent such as benzene, toluene or xylene; an alcohol solvent such as methanol or ethanol; ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and ethylene. An ether solvent such as alcohol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether or diethylene glycol butyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate An ester solvent such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate or ethyl 3-ethoxypropionate; a ketone solvent such as methyl ethyl ketone or acetone.

Preferably, the solvent (E) may be a single one of diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or ethyl 3-ethoxypropionate or both.

The solvent (E) is used in an amount of from 200 parts by weight to 1,500 parts by weight, based on the total amount of the alkali-soluble resin (A), and is preferably from 250 parts by weight to 1200 parts by weight, and more preferably 300 parts by weight. Parts to 1000 parts by weight.

Novolak resin (F)

The photosensitive resin composition of the present invention may optionally contain a novolak resin (F) which can be obtained by polycondensation of a cresol-based aromatic hydroxy compound and an aldehyde compound.

Specific examples of the cresol-based aromatic hydroxy compound may include, but are not limited to, cresols such as m-cresol, p-cresol or o-cresol. a compound; a xylenol compound such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol or 3,4-xylenol. The cresol aromatic hydroxy compound may be used singly or in combination of plural kinds.

Specific examples of the aldehyde compound may include, but are not limited to, A Aldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexane ), furfural, furyllacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzene Formaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chloro Benzaldehyde or cinnamaldehyde. The aldehyde compound may be used singly or in combination of plural kinds.

Preferably, the aforementioned aldehyde compound may be formaldehyde.

The novolak resin (F) may be obtained by polycondensation of another type of aromatic hydroxy compound and an aldehyde compound without affecting the physical properties of the photosensitive resin composition of the present invention.

Specific examples of the other kinds of the above aromatic hydroxy compound may include, but are not limited to, phenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2- An alkyl phenol compound such as a third butyl-5-methylphenol or a 6-t-butyl-3-methylphenol; p-methoxyphenol, m-methoxyphenol, p- Alkoxyphenol such as ethoxyphenol, m-ethoxyphenol, p-propoxyphenol or m-propoxyphenol (alkoxy) Phenol compound (isopropenyl phenol), isopropenyl phenol, p-isopropenyl phenol, 2-methyl-4-isopropenyl phenol or 2-ethyl-4-isopropenyl phenol a compound; an aryl phenol compound such as phenyl phenol; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, and hydroquinone ( Hydroquinone) or a polyhydroxyphenol compound such as pyrogallol.

More preferably, the novolac resin (F) can also be obtained by the following According to the method, a condensation reaction is carried out in the presence of a catalyst and under normal pressure, and unreacted monomers are removed by a dehydration treatment. Wherein, the catalyst may comprise an organic acid or an inorganic acid such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or p-toluenesulfonic acid.

The total amount used based on the alkali-soluble resin (A) is 100% by weight. The novolak resin (F) may be used in an amount of 2 parts by weight to 12 parts by weight, preferably 2.5 parts by parts to 11 parts by weight, and more preferably 3 parts by weight to 10 parts by weight.

When the photosensitive resin composition of the present invention contains a novolac resin (F), the resulting photosensitive resin composition may have less residue.

The aforementioned novolak resin (F) may have a weight average molecular weight of 500 to 3,000.

When the present invention contains a novolak resin (F) and the weight average molecular weight thereof is in the above range, the resulting photosensitive resin composition can further improve the residue phenomenon.

Additive (G)

According to the required physical properties and chemical properties, the photosensitive resin composition can be Further comprising an additive. The selection of such additives is well known to those of ordinary skill in the art to which the invention pertains.

Specific examples of the additive (G) of the present invention may include a filler, A polymer compound other than the alkali-soluble resin (A), an ultraviolet absorber, an anti-aggregation agent, a surfactant, an adhesion promoter, a storage stabilizer, a heat resistance promoter, and the like.

Specific examples of the aforementioned filler may include, but are not limited to, glass or aluminum Wait.

a polymer compound other than the alkali-soluble resin (A) Specific examples may include, but are not limited to, polyvinyl alcohol, polyethylene glycol monoalkyl ether or polyfluoroalkyl acrylate.

Specific examples of the aforementioned ultraviolet absorber may include, but are not limited to 2-(3-Terbutyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide or alkoxybenzophenone.

Specific examples of the aforementioned anti-agglomerating agent may include, but are not limited to, polypropylene Sodium and so on.

The aforementioned surfactant can promote the composition of the photosensitive resin The coating property, and specific examples thereof may include, but are not limited to, a fluorine-containing surfactant or an organic barium surfactant.

The fluorosurfactant can be at the end, main chain or side chain to Containing less fluoroalkyl or fluoroalkenyl, and specific examples thereof may include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2, 2-tetrafluorooctylhexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexa Fluoropentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, perfluorinated ten Sodium dialkyl sulfate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, fluorine Sodium alkane sulfonate, sodium fluorocarbonate, sodium fluorocarbonate, fluoroalkane polyoxyethylene ether, diglycerol tetrakis(fluoroalkane polyoxyethylene ether), fluoroalkylammonium iodine, halothane betaine, halothane Polyoxyethylene ether, perfluoroalkane polyoxyethylene ether or perfluoroalkyl alkanol.

The fluorosurfactant may also be a commercially available product, for example: BM Products manufactured by CHEMIE and available in models such as BM-1000 or BM-1100; products manufactured by Dainippon Ink and Chemical Industries, and can be modeled as Megafac F142D, Megafac F172, Megafac F173, Megafac F183, Megafac F178, Megafac F191, Megafac F471 or Megafac F476; etc.; Sumitomo Chemical's products, and its model can be Fluorad FC 170C, Fluorad FC-171, Fluorad FC-430 or Fluorad FC-431, etc.; Asahi Glass products, and its model can be Chlorofluorocarbon S-112, chlorofluorocarbon S-113, chlorofluorocarbon S-131, chlorofluorocarbon S-141, chlorofluorocarbon S-145, chlorofluorocarbon S-382, chlorofluorocarbon SC-101, chlorine Fluorocarbon SC-102, chlorofluorocarbon SC-103, chlorofluorocarbon SC-104, chlorofluorocarbon SC-105 or chlorofluorocarbon SC-106; new products manufactured by Akita Chemicals, and its model can be F Top EF301 , F Top 303 or F Top 352, etc.; products manufactured by NEOSU, and the models can be Ftergent FT-100, Ftergent FT-110, Ftergent FT-140A, Ftergent FT-150, Ftergent FT-250, Ftergent FT-251, Ftergent FTX-251, Ftergent FTX-218, Ftergent FT-300, Ftergent FT-310 or Ftergent FT-400S.

Specific examples of the organic cerium surfactant may include Dow An organic crucible made by Corning Toray Silicone and available in DC 3 Paint Additive (DC 3 PA), DC 7 PA, SH 11 PA, SH 21 PA, SH 28 PA, SH 29 PA, SH 30 PA, SH 190, SH 193, SZ 6032, SF-8427, SF-8428, DC57 or DC 190; etc.; products manufactured by Momentive Performance Materials Inc., and their models can be TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 or TSF-4452, etc.

The surfactant may also use the aforementioned fluorosurfactant or A surfactant other than an organic quinone surfactant.

Other than the fluorine-containing surfactant or organic barium surfactant The surfactant may include, but is not limited to, a polyoxyethylene alkyl ether such as lauryl polyoxyethylene ether, polyoxyethylene stearate or polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ether or polyoxyethylene a polyoxyethylene aryl ether such as n-decyl phenol ether; a polyoxyethylene dialkyl ester such as polyoxyethylene dilauric acid or polyoxyethylene distearic acid; a nonionic surfactant produced by Shin-Etsu Chemical Co., Ltd. The model may be KP341 or the like; a nonionic surfactant manufactured by Kyoeisha Oil Chemical Industry Co., Ltd., and its model may be poly flow No. 57 or poly flow No. 95.

The surfactant can be used alone or in combination with a plurality of use.

The aforementioned adhesion promoter can be used to enhance the adhesion of the substrate. Further, it may preferably be a functional decane crosslinking agent having a carboxyl group, an alkenyl group, an isocyanate group, an epoxy group, an amine group, a fluorenyl group or a halogen.

Specific examples of the adhesion promoter may include p-hydroxyphenyl three Methoxy decane, 3-methacryloxypropyltrimethoxydecane, ethylene triethoxy decane, ethylene trimethoxy decane, vinyl triethoxy decane, vinyl tris (2-methoxy) Ethoxy)decane, γ-isocyanatepropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexane)ethyltrimethoxy Decane, 3-glycidoxydimethylmethoxydecane, 3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N -(2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-chloropropyltrimethoxydecane or 3-chloropropylmethyl Dimethoxy decane and the like. The adhesion promoter may be used alone or in combination of plural kinds.

The aforementioned preservative stabilizer may have a sulfur group, a mercapto group, a hydroquinone group, A functional group such as an amine group, a nitroso group or a nitro group, and the preservation stabilizer may include, but is not limited to, a polyoxide. Specific examples of the preservative stabilizer may include 4-methoxyphenol, (N-nitroso-N-phenyl)hydroxylamine aluminum, and 2,2-thiobis(4-methyl-6-t-butyl group). Phenol) or 2,6-di-tert-butylphenol.

Specific examples of the heat resistance promoter may include, but are not limited to N-(alkoxymethyl)glycolide compound or N-(alkoxymethyl)melamine or the like.

Specific examples of the N-(alkoxymethyl)glycoluric compound may include N,N,N',N'-tetrakis(methoxymethyl)glycoluril, N,N,N',N'-tetrakis(ethoxymethyl)glycoluril, N,N,N',N '-tetrakis (n-propoxymethyl) glycoluril, N, N, N', N'-tetrakis(isopropoxymethyl) glycoluril, N, N, N', N'-tetra (n-butyl) Oxymethyl)glycolide or N,N,N',N'-tetrakis(t-butoxymethyl)glycoluril Wait. The N-(alkoxymethyl)glycolide compound is preferably N,N,N',N'-tetrakis(methoxymethyl)glycoluril.

Specific examples of the N-(alkoxymethyl)melamine may include N,N,N',N',N",N"-hexa(methoxymethyl)melamine, N,N,N',N',N",N"-hexa(ethoxymethyl) Melamine, N, N, N', N', N", N"-hexa(n-propoxymethyl) melamine, N, N, N', N', N", N"-hexa (isopropoxy Methyl) melamine, N, N, N', N', N", N"-hexa(n-butoxymethyl) melamine or N, N, N', N', N", N"-six (Third butoxymethyl) melamine or the like. The N-(alkoxymethyl)melamine may preferably be N,N,N',N',N",N"-hexa(methoxymethyl)melamine.

The N-(alkoxymethyl)melamine can also be made from tri-chemical The product can be made by NIKARAKKU N-2702 or NIKARAKKU MW-30M.

The total amount used based on the alkali resin (A) is 100 weight The additive (G) may be used in an amount of from 0 part by weight to 10 parts by weight, preferably from 0 part by weight to 6 parts by weight, and more preferably from 0 part by weight to 3 parts by weight.

Method for preparing photosensitive resin composition

The method for producing a photosensitive resin composition of the present invention comprises the above alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), and an o-naphthoquinonediazide sulfonate. (D) and the solvent (E) are placed in a stirrer and stirred to uniformly mix into a solution state, and if necessary, a novolak resin (F) or a high score other than the filler or the alkali-soluble resin (A) may be added. An additive (G) such as a sub-compound, an ultraviolet absorber, an anti-agglomerating agent, a surfactant, an adhesion promoter, a storage stabilizer, or a heat resistance promoter.

Method for manufacturing spacer or protective film

In a specific embodiment of the present invention, the method for producing a spacer or a protective film includes at least the following steps: (a) applying the photosensitive resin composition of the present invention onto a substrate to form a film; (b) emitting radiation At least a portion of the film is irradiated; (c) developed after radiation irradiation; and (d) heated after development, as described below.

In the step (a), the photosensitive resin composition of the present invention is formed into a film on a substrate. When the protective film is formed, a pixel layer composed of a red, green, and blue colored layer is first formed on a transparent substrate, and the photosensitive resin composition of the present invention is formed on the pixel layer. When a spacer is formed, a transparent conductive film is formed on a transparent substrate on which a protective film and a pixel layer have been formed, and a film obtained by using the photosensitive resin composition of the present invention is formed on the transparent conductive film.

In a specific example of the present invention, the transparent substrate may be a glass substrate, a resin substrate or the like, and is preferably a glass substrate such as soda lime glass or alkali-free glass. Specific examples of the resin substrate may be polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate or polyimine.

The transparent conductive substrate may be formed by a NESA film (PPG®) formed of tin oxide (SnO ₂ ) on the entire surface of the transparent substrate or having indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). ITO film, etc.

A coating method or a dry film method can be used for the formation of the aforementioned film.

A method of forming a film by a coating method is to apply a solution of the photosensitive resin composition of the present invention to the above-mentioned transparent conductive film, and it is preferred that the transparent conductive film first heats (pre-bake) the coated surface. The solid solution concentration of the solution applied to the photosensitive resin composition of the coating method is from 5 to 50% by weight, preferably from 10 to 40% by weight, and more preferably from 15 to 35 % by weight. The coating method may include, but is not limited to, a spray coating method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an inkjet coating method, and preferably may be a spin coating method or a slit coating method. law.

Next, a method of forming a film by a dry film method is to laminate a photosensitive dry film comprising the photosensitive resin composition of the present invention on a base film.

The aforementioned photosensitive dry film can be stacked and form a photosensitive film after removing the solvent. When the dry film method is carried out, the solid content of the photosensitive resin composition of the present invention may be from 5 to 50% by weight, preferably from 10 to 50% by weight, more preferably from 20 to 50% by weight, And particularly preferably from 30% by weight to 50% by weight. Specific examples of the base film of the photosensitive dry film may be polyethylene terephthalate (PET), polyethylene, polypropylene or polycarbonate or polyvinyl chloride. The base film of the photosensitive dry film preferably has a thickness of from 15 μm to 125 μm , and more preferably from 1 μm to 30 μm .

When the photosensitive dry film is not used, the photosensitive dry film may also be stacked and covered with a cover film. The cover film of the present invention preferably has a release property so that the photosensitive dry film and the cover film are not separated when the photosensitive dry film is not used, but the photosensitive dry film and the cover film can be easily separated when the photosensitive dry film is to be used.

Specific examples of the cover film having the above characteristics may be applied or printed on a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film or a polyurethane film. The thickness of the cover film is preferably from about 5 μm to 30 μm . The cover film may also be a two-layer or three-layer cover film.

A specific method of stacking the film by a dry film method is to heat-bond a transparent photosensitive dry film on a transparent base film.

In the above method, the film is preferably produced by a coating method, and secondarily by a dry film method, and the film is preferably pre-baked. The conditions of the pre-baking treatment may vary depending on the ingredients and the mixing ratio, and are preferably heated at 70 ° C to 120 ° C for 1 minute to 15 minutes.

After the prebaking treatment, the thickness of the film is preferably from 0.5 μm to 10 μm , and more preferably from 1.0 μm to 7.0 μm .

Step (b) irradiates at least a portion of the film with radiation. When a portion of the film is illuminated, it can be covered with a reticle having a predetermined pattern.

Specific examples of the radiation to be exposed may be visible light, ultraviolet light or far infrared light. The wavelength of the radiation is preferably from 250 nm to 550 nm, and more preferably 365 nm.

The exposure amount was measured by the illuminance meter (manufactured by Optical Associates, Inc., and model number is OAI model 356) to measure the intensity of radiation having a wavelength of 365 nm. Exposure is preferably 100J / m ² to 5,000J / m ^2, and more preferably 200J / m ² to 3,000J / m ^2.

Step (c) is developed after radiation irradiation to remove unnecessary portions and form a predetermined pattern.

Specific examples of the developing solution for development may include sodium hydroxide and hydrogen. An inorganic base such as potassium oxide, sodium carbonate, sodium citrate, sodium metasilicate or ammonia; a first-grade fatty amine such as ethylamine or n-propylamine; a second-grade fatty amine such as diethylamine or n-propylamine; a third-stage fatty amine such as an amine, diethylamine methyl, dimethylethylamine or triethylamine; pyrrole, piperidine, N-methylpiperidine, N-methyl 1,8-diazabicyclo [5.4.0] -7-undecene or a tertiary aliphatic acid such as 1,5-diazabicyclo[4.3.0]-5-decene; pyridine, methylpyrimidine, lutidine Or a fourth-order ammonium salt such as quinoline or the like; a fourth-order ammonium salt basic compound such as an aqueous solution of tetramethylammonium hydroxide or tetraethylammonium hydroxide. A water-soluble organic solvent and/or a surfactant such as methanol or ethanol may also be added to the above developer as needed.

The developing method, for example, the dipping method, the impregnation method or the shower method, is preferably developed at room temperature to 180 ° C for about 10 seconds.

The resulting pattern was subjected to steam cleaning for 30 seconds to 90 seconds after development, and air-dried by compressed air or nitrogen.

Step (d) is followed by heating after development, and the prepared film is heated to 100 ° C to 250 ° C with a suitable heater (for example, a hot plate or an oven), and is subjected to 30 minutes to 180 minutes (post baked) ).

The gap body or protective film having the desired pattern prepared as described above has excellent properties such as compressive strength, abrasion resistance of the liquid crystal alignment film, and adhesion of the substrate.

Method for manufacturing liquid crystal display element

The liquid crystal display element of the present invention comprises the aforementioned film. This hair The liquid crystal display device of the present invention preferably forms a spacer body with a photosensitive resin composition and forms a protective film on at least one side, and preferably forms a protective film on both sides of the spacer.

The liquid crystal display element of the present invention can be obtained by the following two methods Manufacturing, as described below.

The first method is to use the aforementioned photosensitive resin composition by The foregoing method is formed on one side or both sides of the first (electrode) transparent substrate having at least one side of the transparent conductive film. Then, an alignment film having liquid crystal alignment properties is formed on the transparent conductive film having the interstitial body and/or the protective film.

In the foregoing substrate, one side of the alignment film is formed inside The side faces are such that the liquid crystal alignment directions of the various alignment films are reversed and arranged in a reverse direction (cell gap). Next, a liquid crystal compound is filled in a cell gap partitioned by a surface of the substrate (alignment film) and a space, and a filling hole is encapsulated to form a liquid crystal cell. Therefore, the liquid crystal display unit can be formed by bonding the vertical polarizing plate or the liquid crystal polarization direction arranged on the surface of one substrate to form a liquid crystal display element having the same alignment direction of the inner and outer surfaces.

The second method is to use the photosensitive resin composition of the present invention. The protective film or the spacer is formed on one side or both sides of the first transparent substrate having the transparent conductive film on at least one side by the first method described above. Then, an ultraviolet curing adhesive is applied along the edge of the substrate. Next, the liquid crystal compound was dropped on the substrate using a liquid crystal dispenser, and the substrate was stacked under vacuum. Next, a liquid crystal display element can be obtained by encapsulating under ultraviolet light and bonding the polarizing plate inside and outside the liquid crystal.

A specific example of the liquid crystal compound may be a nematic liquid crystal or a layer Columnar liquid crystal, and preferably nematic liquid crystal, for example: Shiff base type liquid crystal, oxidized azo type liquid crystal, biphenyl type liquid crystal, phenylcyclohexane type liquid crystal, ester type liquid crystal, terphenyl type liquid crystal, joint Phenylcyclohexane type liquid crystal, pyrimidine type liquid crystal, dioxane polycyclooctane type liquid crystal, dicyclooctane type liquid crystal, pentacyclooctane type liquid crystal, chloride type liquid crystal, cholesterol carbonate or cholesteric liquid crystal cholesteric type liquid crystal. The liquid crystal compound may also include a chiral agent such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate (a product manufactured by Merck & Co., Ltd., and Its model can be a strong induced liquid crystal of C-15 or CB-15).

Polarizing plate or polyethylene can be used on the outside of the liquid crystal display element An alignment film of an alcohol or the like, an "H film" capable of absorbing iodine, or an "H film" provided between the cellulose acetate protective film and the polarizing plate.

Several embodiments are utilized below to illustrate the application of the present invention, It is not intended to limit the invention, and various modifications and changes may be made without departing from the spirit and scope of the invention.

Preparation of alkali soluble resin (A)

The alkali-soluble resin (A) of Synthesis Example A-1 to Synthesis Example A-5 was prepared according to the first table.

Synthesis Example A-1

A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked cone of 1000 ml volume. After introducing nitrogen gas, 5 parts by weight of methacrylic acid (hereinafter abbreviated as MAA), 5 parts by weight of glycidyl methacrylate (hereinafter abbreviated as GMA), and 10 parts by weight of 2-hydroxyethyl methacrylate (10 parts by weight) were added ( Hereinafter, it is abbreviated as HEMA), 30 parts by weight of dicyclopentenyloxyethyl methacrylate (hereinafter abbreviated as FA-513M), 30 parts by weight of benzyl methacrylate (hereinafter abbreviated as BzMA), and 20 parts by weight. Styrene (hereinafter abbreviated as SM), 2.4 parts by weight of 2,2'-azobis(2-methylbutyronitrile) (hereinafter abbreviated as AMBN), and 240 parts by weight of diethylene glycol dimethyl ether (hereinafter referred to as Referred to as Diglyme) to the reaction flask. Next, the above ingredients were slowly stirred, and the solution was heated to 85 °C. After the polycondensation reaction was carried out for 5 hours, the solvent was devolatilized to obtain an alkali-soluble resin (A-1) of Synthesis Example A-1.

Synthesis Example A-2 to Synthesis Example A-5

Synthesis Example A-2 to Synthesis Example A-5 were prepared in the same manner as in the preparation method of the alkali-soluble resin of Synthesis Example A-1 except that Synthesis Example A-2 to Synthesis Example A-5 were changed in alkali solubility. The type and amount of the raw materials in the resin and the polymerization conditions thereof, and the formulation and polymerization conditions are as shown in Table 1, and will not be further described herein.

Preparation of o-n-quinonediazide sulfonate (D-1) having the structure shown in formula (I) Synthesis Example D-1-1

In a dry nitrogen atmosphere, 0.1 mole of the oxime compound having a hydroxyl group represented by the above formula (I-1) and 0.13 mol of o-naphthoquinonediazide-5-sulfonic acid chloride are added to 450 g of γ-butane. In the ester.

Then, 0.14 mol of triethylamine was dissolved in 50 g of 1,4-dioxane to configure a mixed solution. The mixed solution was added dropwise to the aforementioned γ-butyrolactone solution, and the temperature of the solution was prevented from exceeding 35 °C.

After stirring at 30 ° C for 2 hours, the precipitated triethylamine salt was filtered, and the filtrate was poured into water.

Then, the precipitate was collected by filtration, and the precipitate was dried by a vacuum dryer to obtain an ortho-quinonediazide of Synthesis Example D-1-1 having the structure represented by the following formula (I-1-1). Sulfonate (D-1-1) with an esterification rate of 65%:

In the formula (I-1-1), Q ₁ represents Or a hydrogen atom, and the ratio of the two is 1.3:0.7.

Synthesis Example D-1-2

In a dry nitrogen atmosphere, 0.1 mole of the oxime compound having a hydroxyl group represented by the above formula (I-2) and 0.14 mol of o-naphthoquinonediazide-5-sulfonic acid chloride are added to 450 g of γ-butane. In the ester.

Then, 0.154 mol of triethylamine was dissolved in 50 g of 1,4-dioxane to configure a mixed solution. The mixed solution was added dropwise to the aforementioned γ-butyrolactone solution, and the temperature of the solution was prevented from exceeding 35 °C.

After stirring at 30 ° C for 2 hours, the precipitated triethylamine salt was filtered, and the filtrate was poured into water.

Then, the precipitate was collected by filtration, and the precipitate was dried by a vacuum dryer to obtain an ortho-quinonediazide of Synthesis Example D-1-2 having the structure represented by the following formula (I-2-1). Sulfonate (D-1-2) with an esterification rate of 70%:

In the formula (I-2-1), Q ₂ represents Or a hydrogen atom, and the ratio of the two is 1.4:0.6.

Synthesis Example D-1-3

In a dry nitrogen atmosphere, 0.1 mole of the oxime compound having a hydroxyl group represented by the above formula (I-3) and 0.26 mol of o-naphthoquinonediazide-5-sulfonic acid chloride were added to 450 g of γ-butane. In the ester.

Then, 0.28 mol of triethylamine was dissolved in 50 g of 1,4-dioxane to configure a mixed solution. The mixed solution was added dropwise to the aforementioned γ-butyrolactone solution, and the temperature of the solution was prevented from exceeding 35 °C.

After stirring at 30 ° C for 2 hours, the precipitated triethylamine was filtered off. Salt and pour the filtrate into the water.

Then, the precipitate was collected by filtration, and the precipitate was dried by a vacuum dryer to obtain an ortho-quinonediazide of Synthesis Example D-1-3 having the structure represented by the following formula (I-3-1). Sulfonate (D-1-3) with an esterification rate of 65%:

In the formula (I-3-1), Q ₃ represents Or a hydrogen atom, and the ratio of the two is 1.3:0.7.

Synthesis Example D-1-4

In a dry nitrogen atmosphere, 0.1 mole of the oxime compound having a hydroxyl group represented by the above formula (I-3) and 0.28 mol of o-naphthoquinonediazide-5-sulfonic acid chloride were added to 450 g of γ-butane. In the ester.

Then, 0.33 mol of triethylamine was dissolved in 50 g of 1,4-dioxane to configure a mixed solution. The mixed solution was added dropwise to the aforementioned γ-butyrolactone solution, and the temperature of the solution was prevented from exceeding 35 °C.

After stirring at 30 ° C for 2 hours, the precipitated triethylamine salt was filtered, and the filtrate was poured into water.

Then, the precipitate was collected by filtration, and the precipitate was dried by a vacuum dryer to obtain an ortho-quinonediazide of Synthesis Example D-1-4 having the structure represented by the following formula (I-4-1). Sulfonate (D-1-4) with an esterification rate of 70%:

In the formula (I-4-1), Q ₄ represents Or a hydrogen atom, and the ratio of the two is 1.4:0.6.

Preparation of novolak resin (F)

The novolak resin (F) of Synthesis Example F-1 to Synthesis Example F-4 was prepared according to the second table.

Synthesis Example F-1

A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-neck reaction flask having a volume of 1000 ml. After introducing nitrogen gas, 0.7 mol of m-cresol, 0.3 mol of p-cresol, 0.65 mol of formaldehyde, and 0.01 mol of oxalic acid were added to the reaction flask. Then, the above ingredients were slowly stirred, and the solution was heated to 100 °C. After the polycondensation reaction was carried out for 6 hours, the solution was heated to 180 ° C and dried under reduced pressure at a pressure of 10 mmHg. After the solvent was removed, the novolak resin (F-1) of Synthesis Example F-1 was obtained. The weight average molecular weight of the obtained novolac resin is measured by a method well known to those skilled in the art to which the present invention pertains, and the results are shown in Table 2.

Synthesis Example F-2 to Synthesis Example F-4

Synthesis Example F-2 to Synthesis Example F-4 The same preparation method as that of the novolak resin of Synthesis Example F-1 was used, except that Synthesis Example F-2 to Synthesis Example F-4 were used to change the novolac. The type and amount of the raw materials in the resin and the polymerization conditions thereof, and the formulation, polymerization conditions, and weight average molecular weight are shown in Table 2, and will not be further described herein.

Preparation of photosensitive resin composition

The photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 3 were prepared according to Table 3 below.

Example 1

100 parts by weight of the alkali-soluble resin (A-1) obtained in the above Synthesis Example A-1, 30 parts by weight of tripentaerythritol heptaacrylate (hereinafter abbreviated as B-1-1), and 15 parts by weight of 1-[ 4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylhydrazinyl) (hereinafter abbreviated as C-1), 1 part by weight of the aforementioned synthesis example D-1- 1 ortho-nene diazide sulfonate (D-1-1) and 2 parts by weight of the novolak resin (F-1) obtained in the above Synthesis Example F-1 are added to 200 parts by weight of propylene glycol In the methyl ether acetate (hereinafter abbreviated as E-1), the photosensitive resin composition of Example 1 was obtained by stirring and dissolving. The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 3, wherein the resolution and the method for detecting the residue are described later.

Example 2 to Example 12 and Comparative Example 1 to Comparative Example 3

Examples 2 to 12 and Comparative Examples 1 to 3 were prepared in the same manner as in the production method of the photosensitive resin composition of Example 1. The method differs in that Example 2 to Example 12 and Comparative Example 1 to Comparative Example 3 change the kind and amount of the raw material in the photosensitive resin composition, and the formulation and evaluation results are shown in Table 3. This will not be repeated.

Evaluation method Resolution

The photosensitive resin compositions obtained in the above-described Examples 1 to 10 and Comparative Examples 1 to 3 were applied by spin coating to a 100 mm × 100 mm × 0.7 mm plain glass substrate, respectively. Prebaked at about 4 μm for about 150 seconds at 90 ° C.

Then, the prebaked coating film was placed under the specified mask pattern, and irradiated with ultraviolet light having an energy of 60 mJ/cm ² (exposure machine model AG500-4N, which is manufactured by M&R Nano Technology). Exposure process.

Next, the exposed coating film was immersed in an aqueous solution of potassium hydroxide (KOH) having a concentration of 0.0438% to remove the unexposed portion. After 75 seconds, it was washed with pure water and baked at 235 ° C for 30 minutes to form a cylinder having a specified pattern on the glass substrate.

Thereafter, the minimum diameter of the shape of the cylinder of the interstitial film or the protective film was observed by a scanning electron microscope (SEM) manufactured by Hitachi, Model S-3000N, and evaluated according to the following criteria:

◎: The minimum diameter of the cylindrical shape can be ≦10μm

○: 10 μm < the minimum formable diameter of the cylinder ≦ 15 μm.

△: 15 μm < the minimum formable diameter of the cylinder ≦ 20 μm.

╳: 20 μm < the smallest formable diameter of the cylinder.

2. Residue

The prebaked coating films prepared in the foregoing Examples 1 to 10 and Comparative Examples 1 to 3 were placed under a mask having a prescribed pattern, and were manufactured by an exposure machine (manufactured by Canon, and the model number thereof was PLA-501F) was irradiated with ultraviolet light having an energy of 60 mJ/cm ² . Then, the exposed prebaked coating film was immersed in an aqueous solution of potassium hydroxide having a concentration of 0.0438% at 23 ° C to remove the unexposed portion of the substrate. After 75 seconds, it was washed with pure water and baked at a temperature of 235 ° C for 30 minutes to form a desired photosensitive resin pattern on the glass substrate. Next, the photosensitive resin pattern was observed under a microscope to determine whether or not the unexposed portion had a residue, and was evaluated according to the following criteria:

◎: No residue.

○: Slight residue.

△: A little residue.

╳: There are many residues.

As is apparent from the results of the third table, when the compound (B) having an ethylenically unsaturated group of the present invention contains the first compound (B-1) having a structure represented by the formula (II), the obtained photosensitive material The resin composition has a better resolution.

Next, when the o-naphthoquinonediazide sulfonate (D) contains o-naphthoquinonediazide sulfonate (D-1) having a structure represented by the formula (I), the obtained photosensitivity The resin composition has a high resolution and a small residue.

Further, when the photosensitive resin composition of the present invention further contains a novolak resin (F), the photosensitive resin composition may have less Residue. Here, when the weight average molecular weight of the novolak resin (F) is within the above range, the photosensitive resin composition may have less residue.

It should be noted that the present invention describes the photosensitive resin composition of the present invention and its application by taking specific compounds, compositions, reaction conditions, processes, analytical methods or specific instruments as an example, but any of the technical fields of the present invention have It is to be understood by those skilled in the art that the present invention is not limited thereto, and other compounds, compositions, reaction conditions, processes, and analytical methods may be used for the photosensitive resin composition of the present invention and its application without departing from the spirit and scope of the present invention. Or instrumental.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

Claims (12)

A photosensitive resin composition comprising: an alkali-soluble resin (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); o-naphthoquinonediazide sulfonate (D) ), an o-naphthoquinonediazide sulfonate compound (D-1) having a structure represented by the following formula (I): In the formula (I), R ₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or an alkenyl group; and the R ₂ independently represents a hydrogen atom or has a quinonediazide structure. a functional group; the a, the b, the d and the e respectively represent an integer greater than or equal to 0, and the sum of the f and the g is an integer greater than or equal to 1; when the a, the b, the d, and the When the sum of e is greater than 1, a plurality of R ₁ are the same or different, and when the sum of f and g is greater than 1, at least one of the plurality of R ₂ has a functional group of a quinonediazide structure; and a solvent (E). The photosensitive resin composition as set forth in claim 1, wherein the alkali-soluble resin (A) is composed of an unsaturated carboxylic acid monomer (a1) obtained by copolymerizing an epoxy group-containing unsaturated monomer (a2) and another unsaturated monomer (a3). The photosensitive resin composition as set forth in claim 1, wherein the compound (B) having an ethylenically unsaturated group contains the compound (B-1) having the structure represented by the following formula (II): In the formula (II), R ₃ each independently represents a hydrogen atom or a methyl group; the R ₄ each independently represents a hydrogen atom, an acryloyl group or a methacryl group; and the n represents an integer of 2 to 4 . The photosensitive resin composition as set forth in claim 1 further contains a novolak resin (F). The photosensitive resin composition as disclosed in claim 4, the novolac resin (F) has a weight average molecular weight of 500 to 3,000. The photosensitive resin composition as set forth in claim 1, wherein the total amount of the alkali-soluble resin (A) used is 100. The compound (B) having an ethylenically unsaturated group is used in an amount of 30 parts by weight to 350 parts by weight, and the photoinitiator (C) is used in an amount of 15 parts by weight to 100 parts by weight per part by weight of the ortho-naphthalene. The quinonediazide sulfonate (D) is used in an amount of from 1 part by weight to 16 parts by weight, and the ortho-naphthoquinone diazide sulfonate compound (D-1) having the structure represented by the formula (I) The amount used is from 1 part by weight to 15 parts by weight, and the solvent (E) is used in an amount of from 200 parts by weight to 1500 parts by weight. The photosensitive resin composition as set forth in claim 3, wherein the total amount of the alkali-soluble resin (A) is 100 parts by weight based on the compound of the formula (II) (B- 1) The amount used is from 30 parts by weight to 300 parts by weight. The photosensitive resin composition as set forth in claim 4, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the novolak resin (F) is used in an amount of 2 parts by weight to 12 parts by weight. Parts by weight. A photosensitive resin composition according to any one of claims 1 to 8, which is sequentially subjected to a prebaking treatment, an exposure treatment, a development treatment, and a post-baking treatment. And the gap body having a pattern is produced. A photosensitive resin composition according to any one of claims 1 to 8, which is sequentially subjected to a pre-baking treatment, an exposure treatment, a development treatment, and a post-baking treatment. And the protective film having a pattern is obtained. A liquid crystal display element comprising the interstitial body according to claim 9 of the patent application. A liquid crystal display element comprising the protective film according to claim 10 of the patent application.