KR20010100808A - Photosensitive resin composition, spacer and liquid crystal display element - Google Patents

Abstract

The novel photosensitive resin composition in the case of forming the spacer for liquid crystal display elements by flat plate printing is provided. Specifically, it provides a negative photosensitive resin composition having a conventional characteristic, high sensitivity, and suitable as a material for forming a spacer having excellent developability, alkali resistance, and water resistance without developing residue (scum), and formed of the resin composition. Provided are a spacer and a liquid crystal display device having the spacer.

The photosensitive resin composition of this invention is alkali-soluble resin [A], the compound [B] which has one or more ethylenically unsaturated bonds, the organic peroxide photoinitiator [C] which has a benzophenone structure, and 4,4'-bis (di It contains the photosensitive agent [D] which has an alkylamino) benzophenone structure, and optionally contains the alkali-insoluble vinyl copolymer [A _IS ] which has an epoxy group.

Description

Photosensitive resin composition, spacer and liquid crystal display element

This invention relates to the photosensitive resin composition, the liquid crystal display element spacer which used this material, and a liquid crystal display element.

Conventionally, as a technique of controlling the gap of a liquid crystal display (LCD), the method of spraying spacer particles, such as glass beads and plastic beads, in the middle of two board | substrates, and controlling the thickness of a liquid crystal layer by these sizes is used. . However, this method has the following problems.

1) When the spacer particles are arranged in the effective pixel portion, the pixels in the area portion in which the spacer particles are present do not contribute to the display, so the contrast and the aperture ratio are lowered, and the display quality is lowered.

2) Display defects are caused by damage to the alignment film due to the movement of the spacer particles, aggregation of the spacer particles, and abnormal orientation around the spacer particles.

3) Unevenness of the gap is likely to occur due to the gap between the spacer particle diameters.

4) When the spacer particle diameter becomes small, the panel strength decreases.

In addition, these problems become remarkable as LCDs become larger and higher in size (narrower in gap, higher in resolution).

In order to solve these problems, a method of forming a spacer by plate printing has been proposed. According to this method, a photosensitive resin is apply | coated to a board | substrate, ultraviolet-ray is irradiated through a predetermined mask, and it develops, and can form a dot-shaped and stripe-shaped spacer. According to this, a spacer can be formed in places other than an effective pixel part. Moreover, with this method, since the cell gap can be adjusted by the coating film thickness of the photosensitive resin, control of the gap width is easy, and the precision is high, and the said problem can be solved.

In the process of manufacturing an LCD, the following three methods can be used as a method of providing a spacer and a rubbed alignment film.

(1) A spacer is formed before applying the alignment film, and rubbing is performed after the application.

(2) After applying the alignment film, spacers are formed and rubbing is performed.

(3) A spacer is formed in the rubbed alignment film.

In order to enable the spacer formed by the photosensitive resin to be usable by all the methods of these (1)-(3), the following characteristics are required.

In the plate printing process of forming a spacer, in order to improve the yield,

1) High sensitivity.

2) There is no developing residue (scum) after development.

In the formed spacer,

1) It is equipped with alkali resistance and water resistance in the washing | cleaning process before apply | coating an oriented film.

2) Having solvent resistance with respect to the solvent used for the oriented film.

3) It is equipped with heat resistance which does not produce heat deformation in the baking process of an oriented film.

4) High rubbing resistance to prevent display defects from rubbing.

5) It does not produce a liquid crystal orientation defect, and does not reduce voltage retention and residual DC voltage (residual DC).

SUMMARY OF THE INVENTION The problem to be solved by the present invention is to provide a novel photosensitive resin composition in the case of forming a spacer for liquid crystal display elements by flat printing, and in detail, combines conventional characteristics, is highly sensitive, and develops. It is to provide a negative photosensitive resin composition suitable as a material for forming a spacer having excellent developability and solvent resistance without residues (scum). Moreover, it is providing the spacer and liquid crystal display element formed from the said resin composition.

MEANS TO SOLVE THE PROBLEM The present inventors used alkali-soluble resin [A], the compound [B] which has an ethylenically unsaturated bond, the organic peroxide photoinitiator [C] which has a benzophenone structure, and the 4,4'-bis (dialkylamino) benzophenone structure. The spacer formed using the photosensitive resin composition containing the photosensitive agent [D] which has is excellent in solvent resistance, heat resistance, and rubbing resistance, and does not produce a liquid-crystal orientation defect, and does not reduce voltage retention and residual DC. It also found that it also has achieved the present invention. In addition, the photosensitive resin composition obtained by adding an alkali-insoluble vinyl polymer [A _IS ] having an epoxy group to this system has the same characteristics as the composition, and at the same time, further provides a film having improved alkali resistance and water resistance. Became evident.

The photosensitive resin composition of this invention is shown by following (1)-(12).

(1) alkali-soluble resin [A], compound having ethylenically unsaturated bond [B], organic peroxide photopolymerization initiator [C] having a benzophenone structure and 4,4'-bis (dialkylamino) benzophenone structure A photosensitive resin composition containing a photosensitive agent [D].

(2) The photosensitive resin composition of (1) whose alkali-soluble resin [A] is a copolymer of unsaturated carboxylic monomer (a-1) and other radically polymerizable monomer.

(3) In (2), the other radical polymerizable monomer is a radical polymerizable monomer (a-2) of formula (1), or a radical polymerizable monomer (a-2) and radical polymerizable monomer (a-) of formula (1). 3) [photosensitive resin composition which is a radically polymerizable monomer other than (a-1) and (a-2)].

Formula 1

Where

R ₁ is a hydrogen atom or a methyl group,

R ₂ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,

n is an integer of 0-5.

(4) The photosensitive resin composition of (3) whose n is 1 or 2 in General formula (1).

(5) Photosensitive resin composition as described in (3) or (4) whose R <_1> and R <_2> is a hydrogen atom in General formula (1).

(6) The photosensitive resin composition as described in (2) whose other radically polymerizable monomer is said (a-3).

(7) The photosensitive resin composition in any one of (1)-(6) whose organic peroxide photoinitiator [C] which has a benzophenone structure is a compound of General formula (2).

Formula 2

Where

R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 13 carbon atoms,

X ₁ and X ₂ are each independently —O—, —OO—, or —NH—.

(8) The photosensitive resin composition as described in (7) whose X <_1> and X <_2> are both -O- in general formula (2).

(9) The photosensitive resin composition in any one of (1)-(8) whose compound [B] is a compound which has 3-6 ethylenically unsaturated bonds.

(10) The photosensitive resin composition in any one of (1)-(9) whose ethylenically unsaturated bond of compound [B] is acryloyl group or methacryloyl group.

(11) The photosensitive resin composition in any one of (1)-(10) which further added the alkali-insoluble vinyl polymer [A _IS ] which has an epoxy group.

(12) The polymer or copolymer of the radically polymerizable monomer (a-4) in which the alkali-insoluble vinyl polymer [A _IS ] having an epoxy group has an epoxy group or the radical (a-4) and other radicals according to (11). Photosensitive resin composition which is a copolymer with a polymerizable monomer (a-5).

The film | membrane, spacer, and liquid crystal display element of this invention are shown to following (13)-(16).

(13) A film formed using the photosensitive resin composition according to any one of (1) to (12).

The spacer for liquid crystal display elements formed using the photosensitive resin composition in any one of (14) (1)-(12).

(15) The liquid crystal display element spacer according to (14), wherein the photosensitive resin composition is patterned by plate printing, followed by thermosetting.

(16) A liquid crystal display element having a spacer as described in (14) or (15).

Alkali-soluble resin [A] used for the photosensitive resin composition of this invention is obtained by copolymerizing an unsaturated carboxyl monomer 1 type, or 2 or more types, and another radically polymerizable compound.

As an unsaturated carboxylic monomer (a-1), hereafter ((meth) shows the thing containing both compounds with and without a meth). (Meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, Citraconic acid, mesaconic acid, and the like. These are used alone or in combination.

As another radically polymerizable compound, the radically polymerizable monomer (a-2) of General formula (1) is mentioned first.

Formula 1

Where

R ₁ is a hydrogen atom or a methyl group,

R ₂ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

n is an integer of 0-5.

Next, as radically polymerizable monomers (a-3) other than the said monomer (a-1) and (a-2), Aromatic vinyl compounds, such as styrene, methylstyrene, and vinyltoluene; Unsaturated carboxylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and benzyl (meth) acrylate; 3-cyclohexenylmethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclo [5 · 2 · 1 · 0 ^2.6 ] decanyl (meth (Meth), such as an acrylate, 2,2,6,6- tetramethyl piperidinyl (meth) acrylate, and N-methyl-2,2,6,6- tetramethyl piperidinyl (meth) acrylate Acrylic acid esters; (Meth) acrylamides, such as (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, etc. are mentioned.

Commercially available products include "Biscoat # 193", "East # 320", "Eastern # 2311HP", "Eastern # 220", "Eastern # 2000", "Eastern # 2100", "Osaka Yugigaku Co., Ltd." East # 2150 "," East # 2180 "," East 3F "," East 3FM "," East 4F "," East 4FM "," East 6FM "," East 8F "," East 8FM "," East 17F " , "East 17FM", "East MTG"; "Alonix M-101", "Mine M-102", "Mine M-110", "Mine M-113", "Mine M-117", "Mine M-120" manufactured by Toagosei Co., Ltd., "East M-5300", "East M-5400", "East M-5600", "East M-5700", "East TO-850", "East TO-851", "East TO-1248", " East TO-1249, East TO-1301, East TO-1315, East TO-1317, East TO-981, East TO-1215, East TO-1316, East East TO-1322, copper TO-1342, copper TO-1340, copper TO-1225; Nihon Kayaku Co., Ltd. "KAYARAD R-564", "East R-128H"; "FANCRYL FA-511A", "FA FA-512A", "FA FA-513A", "FA FA-513M", "FA FA-711MM" and "FA FA-712HM" manufactured by Hitachi Chemical Co., Ltd. Etc. can be mentioned. These are used individually or in combination.

It is preferable to use 2 or more types of monomers as other radically polymerizable monomers [radical polymerizable monomers other than (a-1)], and the monomer (a-2) of Formula 1, (a-1), and (a A combination with a radically polymerizable monomer (a-3) which is a monomer other than -2) is more preferable.

Alkali-insoluble vinyl polymer [A _IS ] which has an epoxy group is a radically polymerizable monomer (a-) containing 1 type of polymers or 2 or more types of copolymers of a radically polymerizable monomer (a-4) containing an epoxy group, or an epoxy group. Obtained by copolymerizing 1 type (s) or 2 or more types of 4) with another radically polymerizable compound (a-5).

As a radically polymerizable monomer (a-4) which has an epoxy group, glycidyl (meth) acrylate, 3, 4- epoxy butyl (meth) acrylate, 2-methyl-3, 4- epoxycyclohexyl (meth) acryl The rate etc. are mentioned. These are used individually or in combination. As other radically polymerizable compound (a-5), the unsaturated carboxylic acid monomer (a-1) mentioned above, the radically polymerizable monomer (a-2) of Formula (1), and the radically polymerizable monomer (a-3) ( a-4) is excluded). These are used alone or in combination. As another radically polymerizable compound (a-5), the monomer enumerated in the term of monomer (a-3) can be used.

Alkali-soluble resin [A] mentioned above makes the said unsaturated carboxylic acid monomer and other radically polymerizable monomer a copolymer component, The content can be suitably selected according to the characteristic etc. of the photosensitive resin composition obtained, Usually, copolymer composition The unit contains 5 to 40% by weight of unsaturated carboxylic acid monomer, preferably 10 to 20% by weight and 95 to 60% by weight of other radically polymerizable monomer, preferably 90 to 80% by weight.

If the copolymerized structural unit from the unsaturated carboxylic acid monomer is less than 5% by weight, it is difficult to dissolve in the alkaline developer, and if it exceeds 40% by weight, the solubility in the alkaline developer is too high, and the film roughness tends to occur in the film after development. have.

If the copolymer structural unit from other radically polymerizable monomers is less than 60% by weight, the solubility in the alkaline developer becomes too large, and if it exceeds 95% by weight, it becomes difficult to be dissolved in the alkaline developer.

When the radically polymerizable monomer represented by (a-2) shown in General formula (1) among other radically polymerizable monomers is introduce | transduced into a copolymer, the solubility to aqueous alkali solution increases and the developing time becomes short. Although content in a monomer is 30 weight% or less, when it is 5 weight% or less, the effect of the solubility increase is few, and when it is 30 weight% or more, solubility becomes large too much and a film | membrane roughness arises easily in the film after image development.

Alkali-insoluble vinyl polymer [A _IS ] which has an epoxy group is a 1 type polymerization or 2 or more types of copolymerization of the radically polymerizable monomer (a-4) containing the said epoxy group, or a radically polymerizable monomer (a-) containing an epoxy group. It is obtained by copolymerization of one or two or more of 4) with other radically polymerizable compounds (a-5). Although these content can be suitably selected according to the characteristic etc. of the obtained photosensitive resin composition, the structural unit based on the radically polymerizable monomer (a-4) containing an epoxy group is usually 20-100 weight%, Preferably it is The structural unit based on 50-100 weight% and other radically polymerizable compound (a-5) is 0-80 weight% normally, Preferably it is 0-50 weight%.

When the structural unit based on the radically polymerizable monomer (a-4) containing an epoxy group is less than 20 weight%, or the structural unit based on the other radically polymerizable compound (a-5) exceeds 80 weight%, The alkali resistance of the film obtained by thermosetting after patterning may fall.

Alkali-insoluble vinyl polymer [A _IS ] which has alkali-soluble resin [A] and an epoxy group is obtained by a conventionally well-known polymerization method. The polymerization solvent is methanol, ethanol, 2-propanol, ethyl acetate, butyl acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethyl carbitol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol Monobutyl ether acetate, methyl ethyl ketone, cyclohexanone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, toluene, xylene, γ-butyrolactone, N, N-dimethylacetamide, tetrahydrofuran and the like are preferable. Do. In particular, methanol, ethyl acetate, cyclohexanone, methyl ethyl ketone, and propylene glycol monomethyl ether are preferable. Of course, 2 or more types of mixed solvent may be sufficient.

The polymerization is usually carried out at a monomer concentration of 5 to 50% by weight, a polymerization initiator at 0.01 to 5% by weight, a reaction temperature of 50 to 160 ° C, and a reaction time of 3 to 12 hours. In order to adjust molecular weight, you may add chain transfer agents, such as thioglycolic acid. After the completion of the reaction, the polymerization liquid is used as it is or a reaction liquid is introduced into a large amount of non-solvent to remove oligomers and unreacted monomers, and the resulting precipitate is dried as a resin composition for the photosensitive resin composition. In the case where the polymerization solution is added to a large amount of non-solvent and purified, it is preferable to use a mixed solution of methanol and ethyl acetate as a polymerization solvent and to use cyclohexane or an ethyl acetate / cyclochlorohexane mixture as a non-solvent, because it has good dryness. .

Although the molecular weight of alkali-soluble resin [A] and alkali-insoluble vinyl polymer [A _IS ] which have an epoxy group obtained in this way is not specifically limited, Analysis by GPC using N, N- dimethylformamide as a solvent converts polyethylene oxide. The weight average molecular weight (Mw) is preferably 1,000 to 100,000, preferably 2,000 to 30,000.

When the polyethylene oxide equivalent weight average molecular weight (Mw) of the alkali-soluble resin [A] and the alkali-insoluble vinyl polymer [A _IS ] having an epoxy group is less than 1,000, the strength of the film is weak, the film becomes rough during development, and the pattern is peeled off. easy. On the other hand, when it exceeds 200,000, developability and sensitivity may fall, or a residue may remain after image development.

Examples of the compound [B] having one or more ethylenically unsaturated bonds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenyl (meth). (Meth) acrylic acid derivatives such as acrylate and benzyl (meth) acrylate; Hydroxyalkyl esters, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate ; ω-carboxy polycaprolactone mono (meth) acrylate, monohydroxy hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) acrylate, tricyclo [5 · 2 · 1 · 0 ^2.6 ] decanyl (meth) acrylate, 2,2,6,6-tetramethylpiperidinyl (meth) acrylate Monofunctional (meth) acrylate compounds such as N-methyl-2,2,6,6-tetramethylpiperidinyl (meth) acrylate; 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycoldi (meth) acrylate, diethylene glycol di (meth ) Acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycoldi (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethyl Roll propane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dicyclopentanyldi (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol S di (meth) acrylate, hydroxypropyldi (meth) acrylate And polyfunctional (meth) acrylate compounds such as diethylene glycol bishydroxypropyl (meth) acrylate and monohydroxypentaerythritol tri (meth) acrylate.

Moreover, as these compounds, the monofunctional or polyfunctional (meth) acrylate compound of a commercial item can be used as it is. Specifically, "Aronix M-5400", "Mine M-5700", "Mine M-215", "Mine M-220", "Mine M-245" manufactured by Toago Seigagaku Kogyo Co., Ltd., "M-305", "M-309", "M-315", "M-400", "M-450", "M-8060" and "M-8560"; "Biscourt # 295", "East # 300", "East # 360", "East # 400", manufactured by Osaka Yugigaku Kogyo Co., Ltd .; Nippon Kayaku Co., Ltd. "KAYARADTMPTA", "Dong PET-30", "Dong DPHA", "Dong D-310", "Dong DPCA-60"; "FANCRYL FA-511A", "FA FA-512A", "FA FA-513A", "FA FA-513M", "FA FA-711MM" and "FA FA-712HM" manufactured by Hitachi Chemical Co., Ltd. Can be mentioned.

Preferred compounds among the above are trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol Hexa (meth) acrylate, "Alonix M-305", "Copper M-309", "Copper M-400", "Copper M-450", "Biscote # 300", "Copper # 400", " Polyfunctional (meth) acrylate which has three or more double bonds, such as KAYARAD TMPTA "," copper DPHA "," copper D-310 ", and" copper PE3-30 ", etc. are mentioned. These are used individually or in combination.

Examples of the organic peroxide photopolymerization initiator [C] having a benzophenone structure include 4,4'-di (tert-butylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4 ' -Di (tert-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (tert-butylperoxycarbonyl) benzophenone, 3,4 '-Di (methoxycarbonyl) -4,3'-di (tert-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (tert-butylperoxycarbonyl) benzophenone, 3,5,4'-tri (tert-butylperoxycarbonyl) benzophenone, 3,4,5-tri (tert-butylperoxycarbonyl) benzophenone, 3,4,4'-tri ( Tert-butylperoxycarbonyl) benzophenone, 2,3,4-tri (tert-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (tert-butylperoxycarbonyl) Benzophenone, 3,4,4'-tri (tert-amylperoxycarbonyl) benzophenone, 3,4,4'-tri (tert-hexylperoxycarbonyl) benzophenone, 3,4,4 '-Tri (tert-octylperoxycarbonyl) benzophenone, 3,3,4'-tri (tert-cumylperoxycarbonyl) benzophenone, 4-methoxy-2', 4'-di ( Tert-butyl perox Carbonyl) benzophenone, 4-methoxy-2 ', 4'-di (tert-butylperoxycarbonyl) benzophenone, 3-methoxy-2', 4'-di (tert-butylperoxy Carbonyl) benzophenone, 2-methoxy-2 ', 4'-di (tert-butylperoxycarbonyl) benzophenone, 4-ethoxy-2', 4'-di (tert-butylperoxy Carbonyl) benzophenone, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-hexylperoxycarbonyl ) Benzophenone, "BTTB50" which is a commercial item, "BTTB25" (made by Nihon Yushi Co., Ltd.), etc. are mentioned. These are used individually or in combination.

Moreover, it is also possible to use combining the said photoinitiator [C] and another photoinitiator. As another photoinitiator, 2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one, 1-hydroxy cyclohexyl phenyl ketone, 2-methyl- 1 [4- (methylthio) phenyl] -2- Morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -S-triazine are mentioned. As a commercial item, "Irgacure 651", "E. 184", "E. 500", "E. 369", "E. 907", "E. 819" by Ciba Specialty Chemicals Co., Ltd .; "Lucirin TPO" manufactured by BASF Zefen Co., Ltd .; "TAZ-104", "Down 106", "Down 110", "Down 118" by Midoriga Gaku Co., Ltd. are mentioned.

As preferable photoinitiator [C], 3,3'-di (methoxycarbonyl) -4,4'-di (tert-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbon) Nil) -3,3'-di (tert-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (tert-butylperoxycarbonyl ) Benzophenone is mentioned.

Moreover, as a preferable combination of [C] and another photoinitiator, 3,3'-di (methoxycarbonyl) -4,4'-di (tert-butylperoxycarbonyl) benzophenone and "Irgacure 907" Combination of 4,4'-di (methoxycarbonyl) -3,3'-di (tert-butylperoxycarbonyl) benzophenone with "Irgacure 907", 3,4'-di (meth Combination of oxycarbonyl) -4,3'-di (tert-butylperoxycarbonyl) benzophenone with "Irgacure 907", 3,3'-di (methoxycarbonyl) -4,4'-di Combination of (tert-butylperoxycarbonyl) benzophenone with "Irgacure 369", 4,4'-di (methoxycarbonyl) -3,3'-di (tert-butylperoxycarbonyl) benzo Combination of phenone with "Irgacure 369", combination of 3,4'-di (methoxycarbonyl) -4,3'-di (tert-butylperoxycarbonyl) benzophenone with "Irgacure 369", 3, 4,4'-tri (tert-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,4,4'- Combination of tri (tert-butylperoxycarbonyl) benzophenone with "Irgacure 907", 3,4,4'-tri (tert-butylperoxycarbonyl) benzophene Combination of "Irgacure 369" with 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and "Irgacure 907", 3,3', 4,4'-tetra The combination of (tert-butylperoxycarbonyl) benzophenone and "Irgacure 369" is mentioned.

As a photosensitizer [D], 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4, 4'-bis (dihydroxyethylamino) benzophenone etc. are mentioned. Moreover, as a commercial item, "EAB", "EAB-F" by Hodogaya Chemical Co., Ltd., etc. are mentioned. These are used individually or in combination.

The component content ratio of the photosensitive resin composition of this invention expresses effects, such as alkali resistance, 0-50 weight part of alkali-insoluble vinyl polymer [A _IS ] which has an epoxy group remarkably with respect to 100 weight part of alkali-soluble resin [A]. In order to have 5 to 50 parts by weight, preferably 10 to 30 parts by weight, 10 to 200 parts by weight of a compound [B] having one or more ethylenically unsaturated bonds, preferably 30 to 150 parts by weight, and a benzophenone structure 0.1-50 weight part of organic peroxide photoinitiator [C], Preferably 1-30 weight part, and 0.1-30 weight part of photosensitive agent [D] which has a 4,4'-bis (dialkylamino) benzophenone structure. Preferably it is 0.5-20 weight part. When using together an organic peroxide photoinitiator [C] which has a benzophenone structure, and another photoinitiator, it is preferable to use 10-100 weight part of other photoinitiators with respect to 100 weight part of photoinitiators [C].

When the compound [B] having one or more ethylenically unsaturated bonds is less than 10 parts by weight with respect to 100 parts by weight of the alkali-soluble resin [A], the photocuring of the photosensitive resin becomes insufficient, solubility in the developing solution increases and after development Roughness of the film may occur on the surface of the film. On the other hand, even when the compound [B] exceeds 200 parts by weight, the tack on the surface of the film is too large, resulting in roughening of the film in the film obtained after curing, or residue after development.

Crosslinking (curing) reaction of compound [B] having at least one ethylenically unsaturated bond when the organic peroxide photopolymerization initiator [C] having a benzophenone structure is less than 0.1 part by weight based on 100 parts by weight of the alkali-soluble resin [A]. If this does not fully progress and exceeds 50 weight part, developability will fall.

Organic peroxide photopolymerization initiator [C] which has a benzophenone structure when the photosensitizer [D] which has a 4,4'-bis (dialkylamino) benzophenone structure is less than 0.1 weight part with respect to 100 weight part of alkali-soluble resin [A]. ], The sensitization effect is insufficient, the sensitivity is lowered, and roughening of the film after development occurs. On the other hand, if it exceeds 30 parts by weight, the remaining film ratio of the obtained film is lowered.

The photosensitive resin composition of this invention may contain other components other than the said component as needed in the range which does not impair the objective of this invention. As such another component, a coupling agent, surfactant, etc. are mentioned.

A coupling agent is used in order to improve adhesiveness with a board | substrate, 10 weight part or less is added and used with respect to 100 weight part of remaining components (henceforth abbreviated as "solid content") from which the solvent was removed from the said photosensitive resin composition.

As the coupling agent, silane-based, aluminum-based, and titanate-based compounds are used. Specifically, 3-glycidoxy propyl dimethyl ethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-acryloxy propyl dimethyl ethoxy silane, 3-acryl Oxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, Silanes such as 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, aluminum-based compounds such as acetalkoxy aluminum diisopropylate, tetra Titanate compounds such as isopropylbis (dioctylphosphite) titanate.

Surfactant is used in order to improve the wettability, leveling property, and applicability | paintability to a base substrate, and 0.01-1 weight part is added and used with respect to 100 weight part of said photosensitive resin compositions.

As surfactant, silicone type surfactant, acrylic type surfactant, fluorine type surfactant, etc. are used. Specifically, BIC-300, "Bridge 306", "Bridge 335", "Bridge 310", "Bridge 341", "Bridge 344", "Bridge 370" manufactured by BIC Chemie Co., Ltd. Acrylics such as "dong 354", "east 358", and "east 361"; And fluorine-based compounds such as "SC-101" manufactured by Asahi Glass Co., Ltd., "EF-351" manufactured by Tochem Products Co., Ltd., and "Copper 352".

The photosensitive resin composition of this invention is melt | dissolved in a suitable solvent normally, and is used in a solution state. This solution is prepared by dissolving an alkali-insoluble vinyl polymer [A _IS ] having an alkali-soluble resin [A] and an epoxy group in a solvent and completely dissolving the compound. [B] and benzo having one or more ethylenically unsaturated bonds in the solution. An organic peroxide photopolymerization initiator [C] having a phenone structure, a photosensitive agent [D] having a 4,4'-bis (dialkylamino) benzophenone structure, and a coupling agent, a surfactant, and the like, if necessary, are mixed in a predetermined ratio, It is obtained by preparing to have a solid content concentration of 10 to 50% by weight, then stirring and dissolving completely.

As a solvent used at this time, methoxy diethanol, ethoxy ethanol, 1-methoxy-2-propanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol dimethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, ethyl lactate, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and the like. These solvents can be used individually or in mixture of 2 or more types.

When the photosensitive resin composition solution prepared as mentioned above is apply | coated to the board | substrate surface, and a solvent is removed by heating, a film can be formed.

Application | coating of the photosensitive resin composition solution to a board | substrate surface can be performed by conventionally well-known methods, such as a spin coating method, a roll coat method, and an immersion method.

Subsequently, this film is heated by a hot plate, an oven or the like (hereinafter abbreviated as "preliminary baking"). Although prebaking conditions differ according to the kind and compounding ratio of each component, they are 1 to 5 minutes in a hotplate, and 5 to 15 minutes in an oven at 70-110 degreeC normally.

The liquid crystal display element spacer of the present invention is formed on the electrode substrate for liquid crystal display element described above, and then irradiated with ultraviolet rays or the like through a photo mask of a predetermined pattern, and then developed by a developer, It is obtained by removing unnecessary parts. In addition, the formation method of a spacer is mentioned later in detail in the description about the liquid crystal display element of this invention.

As a developing solution, Inorganic alkalis, such as sodium carbonate, sodium hydroxide, potassium hydroxide; Aqueous solutions, such as organic alkalis, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, are mentioned. Moreover, it is also possible to add methanol, ethanol, surfactant, etc. in an appropriate amount to the said alkali aqueous solution, and to use.

The developing method may be any of dipping, showering, spraying, and the like, and the developing time is usually 30 to 240 seconds. After development, the pattern can be rinsed with running water and dried.

Thereafter, the pattern is heated by a hot plate, oven, or the like (hereinafter abbreviated as "after-baking") to further crosslink unreacted powder of compound [B] having one or more ethylenically unsaturated bonds. The solvent can be completely removed to obtain a predetermined film pattern.

The post-firing conditions vary depending on the type and the blending ratio of each component, but usually at 180 to 250 ° C for 5 to 30 minutes for a hot plate and for 30 to 90 minutes for an oven.

The liquid crystal display element of this invention is characterized by the spacer provided with the photosensitive resin composition of this invention mentioned above. The manufacturing method of this liquid crystal display element is demonstrated.

Inside the upper and lower substrates, a transparent conductive electrode (for example, indium-tin oxide (IT0) and tin oxide (SnO _x )) and an alignment treatment surface or an alignment film (hereinafter referred to as an alignment film) are stacked in this order. Furthermore, after forming the film of the photosensitive resin composition of this invention so that it may become a target thickness between the surface of the oriented film on these one or both laminated substrates, or between an oriented film and an electrode substrate, for example, 5 micrometers x 5 micrometers-15 micrometers x Radiation is irradiated through the photomask in which the pattern with a 15 micrometers grating | transmission part is partitioned, and after that, the film of a non-irradiation part is removed by image development, and baking is performed and parts other than the opening part of a liquid crystal panel are performed. The spacer which became a grid | lattice form by the cured film of columnar shape (pillar shape of the photosensitive resin composition) is formed in (for example, between pixels).

Although the shape of the said spacer is not specifically limited, When viewed from the top, it is preferable that it is square, rectangular, circular, and elliptical, and in the case of rectangular and elliptical, it is preferable that the long-axis direction is horizontal or orthogonal to a rubbing direction. Moreover, when viewed from the side, it is square, rectangular, trapezoid, and trapezoid is especially preferable. In addition, the angle of the upper part of a trapezoid may be rounded, and the lower part of a trapezoid may be attracted to a hem. The trapezoidal shape is particularly effective when the alignment film is applied and rubbed on the spacer, when the alignment film is uniformly applied or when the rubbing treatment is performed uniformly.

As a board | substrate, the synthesis of transparent glass substrates, such as a white plate glass, a blue plate glass, a silica coated blue plate glass, polycarbonate, polyester, an acrylic resin, a vinyl chloride resin, an aromatic polyamide resin, a polyamideimide, a polyimide, etc. Metal substrates, such as a resin sheet, a film or a board | substrate, an aluminum plate, a copper plate, a nickel plate, and a stainless plate, other ceramic plates, the semiconductor substrate which has a photoelectric conversion element, etc. are mentioned. These substrates can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, and the like, in some cases.

When apply | coating a photosensitive resin composition to a board | substrate, it can carry out by a conventionally well-known method, such as a spin coating method, a roll coat method, and an immersion method.

Drying of the film after application can be performed by blowing air superheated with respect to a film, or placing a board | substrate on a superheated hotplate. The heating temperature of a dry wind or a hotplate is 30-300 degreeC normally, Especially preferably, it is 50-200 degreeC. The heating time is preferably 1 to 30 minutes, and the heating temperature may be kept constant, but may be increased in stages. The film thickness after drying is 0.1-10 micrometers normally, Preferably it is 1-7 micrometers.

As the radiation used when forming the spacer, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like can be used. Especially preferably, the radiation is in the range of 190 nm to 450 nm. The irradiation energy of the radiation is preferably 1 to 1000 mJ / cm 2.

As a developing solution, aqueous solutions, such as inorganic alkalis, such as sodium carbonate, sodium hydroxide, potassium hydroxide, and organic alkalis, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, are mentioned. Moreover, it is also possible to add methanol, ethanol, surfactant, etc. in an appropriate amount to the said alkali aqueous solution, and to use.

The developing method may be any of dipping, showering, spraying, and the like, and the developing time is usually 30 to 240 seconds. After development, the pattern can be rinsed with running water and dried.

The spacer formed in this way may be a spot shape or a line shape. Moreover, it is also possible to disperse | distribute and fix the bead which has conventionally been used in the said resin film, and to use. In addition, the photosensitive resin composition is applied onto a glass substrate, and patterned in the same manner, leaving only the periphery of the substrate, leaving the composition, and assembling the liquid crystal cell so as to face another substrate thereon, pressing and firing the substrate. The composition can be assembled into the liquid crystal element as a sealing material. Moreover, you may form the film | membrane which performs an orientation process on the said resin film.

The liquid crystal display element is manufactured by integrating the positions of the upper and lower element substrates formed as described above, followed by heat treatment after compression, and then injecting a liquid crystal to seal the injection port. Further, after spreading the liquid crystal onto the liquid crystal element substrate, the substrate may be laminated to seal the liquid crystal so as not to leak to produce a liquid crystal display element. In this way, the spacer which has the outstanding liquid crystal resistance formed from the photosensitive resin composition of this invention can be existed in a liquid crystal display element.

It does not specifically limit as a liquid crystal used for the liquid crystal display element of this invention, ie, a liquid crystal compound and a liquid crystal composition, Any of a liquid crystal compound and a liquid crystal composition can also be used.

As an orientation-treated surface and an orientation film used for the liquid crystal display element of this invention, if the orientation of a liquid crystal molecule is regulated, it will not specifically limit, Any inorganic substance or organic substance may be sufficient. In general, polyimide-based and polyamide-based resins are frequently used. More specifically, as the alignment film The alignment film which has a structural unit of (wherein G is a divalent aromatic group or an aliphatic group; Y represents an organic group such as a tetravalent aromatic group, an aliphatic group, or an aliphatic group having a 4, 5 or 6 membered ring structure) is preferable. Do.

Specific examples of the divalent organic group G include

Wherein R ₈ represents H or an alkyl group having 1 to 10 carbon atoms; R ₉ represents an alkylene group having 1 to 10 carbon atoms; n represents an integer of 1 to 3; m represents 1 or 2 Can be mentioned.

Specific examples of the tetravalent organic group Y include

And (wherein R ₈ represents H or an alkyl group having 1 to 10 carbon atoms, n represents an integer of 0 to 4, and m represents 0 or 1).

Example

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

(Manufacture of alkali-soluble resin [A])

Alkali-soluble resins [A-1] to [A-8] used in the examples and the comparative examples are prepared as follows.

Alkali-soluble resin (A-1):

In a separate flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer, 20 g of methacrylic acid as the unsaturated carboxylic acid monomer (a-1) and 130 g of benzyl methacrylate as the other radically polymerizable compound (a-3) and 2 20 g of hydroxyethyl acrylate, 30 g of 5-tetrahydrofurfuryloxycarbonylpentyl acrylate ("KAYARADTC-110S" manufactured by Nihon Kayaku Co., Ltd.) as a radical polymerizable compound (a-2) of Formula 1, and polymerization 1 g of 2,2'-azobisisobutyronitrile as an initiator, 3 g of thioglycolic acid as a chain transfer agent, 167 g of methanol and 333 g of ethyl acetate are added as a solvent. Thereafter, air in the flask is removed with nitrogen for 30 minutes, and the flask is maintained in an oil bath at 65 ° C. for 6 hours to carry out the polymerization reaction.

Thereafter, 3,000 g of cyclohexane was added to the polymerization solution to precipitate the polymer, the supernatant was decanted, and then vacuum dried at 40 ° C. for 20 hours to obtain 180 g of an alkali-soluble resin (A-1).

The polyethylene oxide equivalent weight average molecular weight of obtained alkali-soluble resin is 7,000 (refer Table 1).

Alkali-soluble resins (A-2) to (A-8):

As shown in Table 1, alkali monomer-soluble resins (A-2) to (A-8) are obtained in the same manner as (A-1) by changing the ratio of monomer components. Table 1 shows the yield and the molecular weight of the obtained resin.

(Preparation of alkali insoluble polymer [A _IS ])

Alkali-insoluble polymers [A _IS- 1] to [A _IS- 4] used in Examples and Comparative Examples are prepared as follows.

Alkali Insoluble Polymer [A _IS- 1]

In a separate flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, 160 g of glycidyl methacrylate as a radical polymerizable monomer having an epoxy group and 40 g of methyl methacrylate as another radical polymerizable compound (a-5) 8 g of 2,2'-azobisisobutyronitrile as a polymerization initiator and 800 g of methyl ethyl ketone are added as a solvent. Thereafter, air in the flask was removed with nitrogen for 30 minutes, and the flask was kept in an oil bath at 80 ° C. for 6 hours to carry out a polymerization reaction.

Thereafter, 3,000 g of cyclohexane was added to the polymerization solution to precipitate the polymer, the supernatant was decanted, and then vacuum dried at 40 ° C. for 20 hours to obtain an alkali insoluble polymer (A _IS- 1).

The polyethylene oxide equivalent weight average molecular weight of obtained alkali-soluble resin is 6,100 (refer Table 2).

Alkali insoluble polymer [A _IS -2] to [A _IS -4]

As shown in Table 2, the proportion of the monomer component is changed to be the same as in (A _IS- 1) to obtain an alkali insoluble polymer. The molecular weight of the obtained resin is shown in Table 2.

Below, the manufacture of the photosensitive resin composition, its performance evaluation, the manufacture of the spacer and liquid crystal display element using this, and the result of having performed these evaluation are demonstrated in the following Example.

(Production of Photosensitive Resin Composition)

(Example 1)

After dissolving 100 parts by weight of alkali-soluble resin (a-1) by mixing 200 parts by weight of propylene glycol monomethyl ether acetate, and dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as compound [B] in the obtained solution. 100 parts by weight of a mixture of Toago Seigagaku Kogyo Co., Ltd. "Alonics M400"}, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzo as photopolymerization initiator [C] 10 parts by weight of a 25% by weight toluene solution of phenone {"BTTB25" (manufactured by Nihon Yushi Co., Ltd.)} (solid content) and 4,4'-bis (diethylamino) benzophenone as a photosensitive agent [D] 1 part by weight of "EAB-F"}, and 0.3 parts by weight of a silicone-based surfactant ("Byk-344" manufactured by BIC Chemie Zepen Co., Ltd.) as other components, and the solid content concentration of this mixed solution is 39 Propylene glycol monomethyl ether acetate is added to the weight percent, after which the mixture is stirred until a homogeneous solution is obtained. On the other hand, the membrane filter having a pore diameter of 0.22 탆 is filtered to obtain a solution of the photosensitive resin composition.

(Examples 2 to 46)

Except having added the predetermined amount of each component of Tables 3-5, it carries out like Example 1 and obtains the photosensitive resin composition.

(Comparative Example 1)

Photoinitiator [C] is 30 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ("Irgacure 369" manufactured by Ciba Specialty Chemicals Co., Ltd.) , A solution was prepared in the same manner as in Example 1 except that the photosensitive agent [D] was not used.

(Comparative Example 2)

The polymerization initiator [C] was 2,4,6-trimethyrelbenzoyldiphenylphosphine oxide (BASF Zepen Co., Ltd. "Lucirin TPO") 30 parts by weight, except that no photosensitive agent [D] was used. A photosensitive resin composition solution is prepared in the same manner as 1.

(Example 47)

100 weight part of alkali-soluble resin (a-1), 15 weight part of alkali insoluble polymers (A _IS- 1), and 250 weight part of propylene glycol monomethyl ether acetates were mixed and dissolved, and it was dipentaerythritol hexaacryl as a compound [B]. 60 parts by weight of a mixture of latex and dipentaerythritol pentaacrylate ("Aronix M400" manufactured by Toago Seigagaku Kogyo Co., Ltd.), 3,3 ', 4,4'-tetra (class 3) as a photopolymerization initiator [C] 6 parts by weight of a 25% by weight toluene solution of butylperoxycarbonyl) benzophenone ("BTTB25" manufactured by Nippon Yushi Co., Ltd.) (solid content), 4,4'-bis (diethylamino) benzo as a photosensitizer [D] 3 parts by weight of phenone ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) and 0.3 parts by weight of a silicone-based surfactant ("Byk-344" manufactured by BIC Chemie Zepen Co., Ltd.) as other components, Propylene glycol monomethyl ether acetate is added so that the concentration is 39% by weight. Thereafter, the mixture is stirred until a uniform solution is obtained, and filtered through a membrane filter having a pore diameter of 0.22 µm to obtain a solution of the photosensitive resin composition.

(Examples 47 to 80)

Except having added predetermined amount each component of Table 6 and 7, it carries out like Example 47 and obtains the photosensitive resin composition.

The abbreviated-name in Tables 3-7 is demonstrated below.

Compound [B]:

B-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("Alonix M-400" manufactured by Toagosei Chemical Co., Ltd.)

B-2: trimethylolpropane triacrylate ("Aronix M-309" made by Toago Seigagaku Kogyo Co., Ltd.))

B-3: pentaerythritol triacrylate ("Alonix M-305" made by Toagosei Chemical Co., Ltd.)

B-4: pentaerythritol tetraacrylate ("Aronix M-450" made by Toago Seigagaku Kogyo Co., Ltd.)

Photopolymerization initiator [C]:

C-1: 25 wt% toluene solution of 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone ("BTTB25" manufactured by Nihon Yushi Co., Ltd.)

C-2: 25 wt% toluene solution of 3,4,4'-tri (tert-butylperoxycarbonyl) benzophenone

C-3: 20 wt% toluene solution of 3,3'-di (methoxycarbonyl) -4,4'-di (tert-butylperoxycarbonyl) benzophenone

C-4: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-("Irgacure 369" made by Ciba Specialty Chemicals Co., Ltd.)

C-5: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

(BASF Zepen Co., Ltd. "Lucirin TPO")

Photosensitizer [D]:

D-1: 4,4'-bis (diethylamino) benzophenone (made by Hodogaya Chemical Co., Ltd. "EAB-F")

D-2: 4,4'-bis (dimethylamino) benzophenone

Other Ingredients (Surfactants):

E-1: Silicone type surfactant ("Byk-344" made by BIC Chemie Zepen Co., Ltd.)

Other Ingredients (Coupling Agents):

F-1: 3-methacryloxypropyl trimethoxysilane ("Syirasu S710" made by Chisso Corporation)

Using the photosensitive resin composition obtained in the said Example, a film and a spacer are formed and the performance is evaluated. The method and results are described below.

Photosensitive resin composition evaluation (formation of a spacer):

Formation method of spacer (a)

The photosensitive resin composition solutions obtained in Examples and Comparative Examples were distributed on a glass substrate / or a glass substrate with a transparent electrode made of an ITO film, and spun for 15 seconds at 900 rpm, followed by a hot plate at 90 ° C., 3 Prebaking for a minute forms a film.

Then, the obtained film is exposed through the photomask which forms a grid pattern pattern by the light transmission part of 10 micrometers x 10 micrometers using PLA-501F mask aligner (made by Canon Corporation). In addition, exposure is performed in the whole line (without a filter) in air | atmosphere, and it irradiates the ultraviolet-ray of 100 mJ / cm <2> of exposure amount. Accumulated photometer UIT-102 (made by Ushio Corporation) is used for the measurement of an exposure amount, and a light receiver uses UVD-365PD (made by Ushio Corporation). Subsequently, after developing predetermined time (30-120 second) (shower image development, shower pressure 0.04 MPa) at 23 degreeC using 0.05 weight% potassium hydroxide aqueous solution, it washes with pure water for 15 second, and rinses and dries. Furthermore, it heat-fires at 200 degreeC for 30 minute (s) in oven, and forms the spacer of 5 micrometers thickness patterned by the cured film of the 10 micrometers x 10 micrometers columnar photosensitive resin composition in grid pattern shape on a board | substrate.

Formation method of spacer (b)

Spin coating is carried out at a rotational speed of 1000 rpm, and the coating is carried out as in the formation method (a) except that the film thickness is changed to 4.8 µm.

Formation method of spacer (c)

The exposure was carried out in the same manner as the formation method (a) except that the exposure amount was changed to ultraviolet irradiation of 200 mJ / cm 2.

The following physical properties of the spacer (film) obtained as described above were measured.

·Sensitivity:

In the spacer obtained as described above, the residual film ratio ((film thickness after development / film thickness after preliminary development) x 100) after the development for 40 seconds and the residual film ratio of the obtained film were measured and judged by the following criteria. .

○… Residual rate is over 90%

×… Residual rate is less than 90%

Developability:

In the case where the spacer is formed as described above (observed at 10,000 times using a scanning electron microscope), the time when the film disappears, that is, the development time, is evaluated based on the following criteria.

◎… Developing time <40 seconds

○… Developing time 40 to 60 seconds

×… Developing time ＞ 60 seconds

Alkali resistance:

The glass substrate with a bulk pattern of 4 cm x 4 cm obtained as described above was immersed in a 5 wt% sodium hydroxide aqueous solution at 60 ° C. for 10 minutes, and then the checkerboard scale tape method (JIS K5400, Clause 8.5.2, cross Adhesion test using 1 mm ² × 100 cross cut guides) was carried out, and the change of the film surface was observed with a change rate of the film thickness before and after the immersion treatment and a 400 times optical microscope. It is judged on the basis of.

○… There is no peeling by the checkerboard graduation tape method, and the change rate of the film thickness is less than 5%, and there is no change in the film surface before and after treatment.

×… When other than the above

Water resistance:

After the glass substrate with a bulk pattern of 4 cm × 4 cm obtained as described above, the immersion treatment was performed separately using immersion treatment at 80 ° C. for 1 hour and ultrasonic cleaning at 60 ° C. for 1 hour in ultrapure water. , Adhesion test by the checker scale method (JIS K5400, Clause 8.5.2, 1mm ² × 100 cross-cut guide) is used, and the surface of the film by the change rate of the film thickness before and after treatment and 400 times optical microscope Observation of the change of and determination based on the following criteria are made.

○… In either treatment, there was no peeling by the checkerboard graduation tape method, the rate of change of the film thickness was less than 5%, and there was no change in the film surface before and after the treatment.

×… Otherwise

Heat resistance:

After reheating the spacer formed on the substrate at 240 ° C. for 1 hour, the residual film ratio ((film thickness after reheating / film thickness after post-baking) × 100) after reheating was measured, and determined according to the following criteria.

○… Remnant rate after reheating is 95% or more

×… Residual rate after reheating is less than 95%

Solvent resistance:

After the spacer formed on the substrate was immersed in N-methyl-2-pyrrolidone for 1 hour at 25 ° C., the change of the film surface was observed by the rate of change of the film thickness before and after the treatment and 400 times optical microscope. The determination is made based on the following criteria.

○… While the rate of change of the film thickness is less than 5%, there is no change in the film surface before and after the treatment.

×… 5% or more change in film thickness

The results are shown in Tables 8-14.

Photosensitive resin composition Formation of film (spacer) Film (Spacer) Properties Way Board Sensitivity Developability Heat resistance Solvent resistance Example 1 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ (b) Glass ○ ◎ ○ ○ (b) ITO / Glass ○ ◎ ○ ○ (c) Glass ○ ◎ ○ ○ (c) ITO / Glass ○ ◎ ○ ○ Example 2 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 3 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 4 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 5 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 6 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 7 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 8 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 9 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 10 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 11 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○

Photosensitive resin composition Formation of film (spacer) Film (Spacer) Properties Way Board Sensitivity Developability Heat resistance Solvent resistance Example 12 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 13 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 14 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 15 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 16 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 17 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 18 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 19 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 20 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 21 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 22 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 23 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○ Example 24 (a) Glass ○ ◎ ○ ○ (a) ITO / Glass ○ ◎ ○ ○

Photosensitive resin composition Formation of film (spacer) Film (Spacer) Properties Way Board Sensitivity Developability Heat resistance Solvent resistance Example 25 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 26 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 27 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 28 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 29 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 30 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 31 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 32 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 33 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 34 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 35 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 36 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 37 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○

Photosensitive resin composition Formation of film (spacer) Film (Spacer) Properties Way Board Sensitivity Developability Heat resistance Solvent resistance Example 38 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 39 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 40 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 41 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 42 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 43 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 44 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Example 45 (a) Glass ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ Comparative Example 1 (a) Glass × × × × (a) ITO / Glass × × × × Comparative Example 2 (a) Glass × × × × (a) ITO / Glass × × × ×

Photosensitive resin composition Formation of film (spacer) Film (Spacer) Properties Way Board Sensitivity Alkali resistance Developability Heat resistance Solvent resistance Example 47 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ (b) Glass ○ ○ ○ ○ ○ (b) ITO / Glass ○ ○ ○ ○ ○ (c) Glass ○ ○ ○ ○ ○ (c) ITO / Glass ○ ○ ○ ○ ○ Example 48 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 49 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 50 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 51 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 52 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 53 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 54 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 55 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 56 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○

Photosensitive resin composition Formation of film (spacer) Film (Spacer) Properties Way Board Sensitivity Alkali resistance Developability Heat resistance Solvent resistance Example 57 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 58 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 59 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 60 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 61 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 62 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 63 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 64 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 65 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 66 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 67 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 68 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○

Photosensitive resin composition Formation of film (spacer) Film (Spacer) Properties Way Board Sensitivity Alkali resistance Developability Heat resistance Solvent resistance Example 69 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 70 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 71 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 72 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 73 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 74 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 75 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 76 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 77 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 78 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 79 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○ Example 80 (a) Glass ○ ○ ○ ○ ○ (a) ITO / Glass ○ ○ ○ ○ ○

Next, the liquid crystal element spacer is manufactured using the photosensitive resin composition of this invention, and the liquid crystal display element of this invention which has the said spacer is manufactured. The embodiment is described below.

Formation of Liquid Crystal Display Devices

(Example 201)

On a glass substrate with a transparent electrode made of an ITO film, a spacer pattern of 10 μm × 10 μm in a lattice shape is vertically 100 μm in a lattice form through the above-described spacer forming method (a), that is, spin coating, prefiring, exposure, development and post-firing processes. The spacer-attached substrates are formed at intervals of 50 μm in width.

Next, after apply | coating a liquid crystal aligning agent ("LIXON aligner PIA-5004" by Chisso Corp.) to the said spacer formation board | substrate, it dried on a hotplate for 70 minutes and 10 minutes, and also 60 minutes at 200 degreeC in oven. The heat treatment is performed to form an alignment film having a film thickness of 0.06 µm on the substrate with spacers.

The rubbing treatment is performed at a rotational speed of 1000 rpm and a step movement speed of 59 mm / second by a rubbing device having a roll wound with a cloth made of nylon.

Furthermore, after apply | coating the epoxy type sealing agent which mixed 2% of glass fiber spacers to the outer edge of the board | substrate with a spacer which has the said orientation-treated oriented film surface, rubbing a pair of board | substrates so that a liquid crystal aligning film surface may face. The laminates are compressed so that the directions are perpendicular to each other, and then thermally cured. Next, liquid crystal for TFT ("FB01" made by Tosso Co., Ltd.) is sealed between the pair of substrates, and then the inlet is sealed with a photocurable resin. Thereafter, an isotropic treatment is performed at 110 ° C. for 30 minutes, and slowly cooled to room temperature to obtain a liquid crystal display device.

The rubbing resistance, liquid crystal orientation, voltage retention, and residual DC of the thus obtained liquid crystal display device were evaluated by the following method.

Rubbing resistance:

On the glass substrate with a transparent electrode which consists of an ITO film | membrane, the spacer pattern of 10 micrometers x 10 micrometers is formed in a grid | lattice form at 100 micrometer-long space | interval and 50 micrometer space | interval as mentioned above.

Next, after apply | coating a liquid crystal aligning agent ("LIXON aligner PIA-5004" by Chisso Corp.) to the said spacer formation board | substrate, it dried on a hotplate for 70 minutes and 10 minutes, and also 60 minutes at 200 degreeC in oven. The heat treatment is performed to obtain a substrate in which an alignment film having a film thickness of 0.06 μm is formed on a spacer.

By the rubbing device which has the roll which rolled up the cloth made from nylon on this oriented film surface, the state at the time of performing a rubbing process at 1000 rpm of rolls and 59 mm / sec of moving speed of a step is determined based on the following reference | standard.

○… Spacer does not cut or peel

×… Otherwise

Liquid crystal orientation:

Confirmation of orientation is performed using a polarizing plate, and the following criteria are determined.

○… Has good orientation

×… Bad orientation

Voltage retention:

The measurement is performed by reading a varying drain with an oscilloscope by applying a square wave having a gate pulse width of 69 μs, a frequency of 60 Hz, and a wave height of ± 4.5 V to the source. This is carried out four times and using the average value, the case where the voltage does not decrease at all is set to 100% and the relative value is used as the voltage retention. In addition, measurement is performed at 60 degreeC.

Residual DC:

The measurement is performed using the C-V curve method. The CV curve method applies a 25 mV and 1 KHz alternating current to the liquid crystal element, superimposes a triangular wave of a direct current with a frequency of 0.0036 Hz, and records the capacitance C changed by sweeping the voltage in the range of -10 to 10 V. Way. In addition, measurement is performed at 60 degreeC.

Table 15 shows the results of the measurement and determination of each characteristic.

(Examples 202 to 236) and (Examples 301 to 334)

As shown in Tables 15 to 17 shown below, the photosensitive resin composition obtained in Examples 2 to 36 or the combination of the photosensitive resin composition obtained in Examples 47 to 80 and the liquid crystal composition was obtained in the same manner as in Example 201. To produce a liquid crystal display device, and the results obtained are shown in Tables 15 to 17.

Example Liquid crystal display elements Display element characteristics Photosensitive resin
Composition LCD
Composition Rubbing resistance Liquid crystal alignment Voltage retention rate [%] Residual DC [V] 201 Example 1 FB01 ○ ○ 97.5 0.29 202 Example 2 LA ○ ○ 97.6 0.20 203 Example 3 LB ○ ○ 97.6 0.22 204 Example 4 LC ○ ○ 97.8 0.18 205 Example 5 LD ○ ○ 97.8 0.20 206 Example 6 LE ○ ○ 97.9 0.18 207 Example 7 FB01 ○ ○ 97.4 0.28 208 Example 8 FB01 ○ ○ 97.5 0.25 209 Example 9 FB01 ○ ○ 97.5 0.23 210 Example 10 FB01 ○ ○ 97.7 0.29 211 Example 11 FB01 ○ ○ 97.5 0.25 212 Example 12 FB01 ○ ○ 97.5 0.29 213 Example 13 FB01 ○ ○ 97.4 0.28 214 Example 14 LA ○ ○ 97.5 0.21 215 Example 15 LB ○ ○ 97.5 0.22 216 Example 16 LC ○ ○ 97.7 0.17 217 Example 17 LD ○ ○ 97.8 0.21 218 Example 18 LE ○ ○ 97.9 0.19 219 Example 19 FB01 ○ ○ 97.6 0.29 220 Example 20 LA ○ ○ 97.6 0.21 221 Example 21 LB ○ ○ 97.6 0.21 222 Example 22 LC ○ ○ 97.8 0.17 223 Example 23 LD ○ ○ 97.9 0.22

Example Liquid crystal display elements Display element characteristics Photosensitive resin
Composition LCD
Composition Rubbing resistance Liquid crystal alignment Voltage retention rate [%] Residual DC [V] 224 Example 24 LE ○ ○ 97.8 0.18 225 Example 25 FB01 ○ ○ 97.6 0.25 226 Example 26 LA ○ ○ 97.5 0.20 227 Example 27 LB ○ ○ 97.6 0.22 228 Example 28 LC ○ ○ 97.7 0.18 229 Example 29 LD ○ ○ 97.8 0.21 230 Example 30 LE ○ ○ 97.7 0.17 231 Example 31 FB01 ○ ○ 97.5 0.29 232 Example 32 LA ○ ○ 97.5 0.21 233 Example 33 LB ○ ○ 97.6 0.22 234 Example 34 LC ○ ○ 97.9 0.17 235 Example 35 LD ○ ○ 97.9 0.22 236 Example 36 LE ○ ○ 97.9 0.18 301 Example 47 FB01 ○ ○ 97.4 0.28 302 Example 48 FB01 ○ ○ 97.5 0.25 303 Example 49 FB01 ○ ○ 97.5 0.23 304 Example 50 FB01 ○ ○ 97.7 0.29 305 Example 51 FB01 ○ ○ 97.5 0.25 306 Example 52 FB01 ○ ○ 97.5 0.29 307 Example 53 FB01 ○ ○ 97.4 0.28 308 Example 54 FB01 ○ ○ 97.4 0.28 309 Example 55 LA ○ ○ 97.6 0.20 310 Example 56 LB ○ ○ 97.6 0.22

Example Liquid crystal display elements Display element characteristics Photosensitive resin
Composition LCD
Composition Rubbing resistance Liquid crystal alignment Voltage retention rate [%] Residual DC [V] 311 Example 57 LC ○ ○ 97.8 0.18 312 Example 58 LD ○ ○ 97.8 0.20 313 Example 59 LE ○ ○ 97.9 0.18 314 Example 60 LA ○ ○ 97.5 0.21 315 Example 61 LB ○ ○ 97.5 0.22 316 Example 62 LC ○ ○ 97.7 0.17 317 Example 63 LD ○ ○ 97.8 0.21 318 Example 64 LE ○ ○ 97.9 0.19 319 Example 65 FB01 ○ ○ 97.6 0.29 320 Example 66 FB01 ○ ○ 97.6 0.21 321 Example 67 FB01 ○ ○ 97.6 0.21 322 Example 68 FB01 ○ ○ 97.8 0.17 323 Example 69 LA ○ ○ 97.5 0.21 324 Example 70 LA ○ ○ 97.5 0.22 325 Example 71 LA ○ ○ 97.7 0.17 326 Example 72 LA ○ ○ 97.8 0.21 327 Example 73 LB ○ ○ 97.9 0.18 328 Example 74 LB ○ ○ 97.5 0.21 329 Example 75 LB ○ ○ 97.5 0.22 330 Example 76 LB ○ ○ 97.7 0.17 331 Example 77 LC ○ ○ 97.8 0.18 332 Example 78 LC ○ ○ 97.8 0.20 333 Example 79 LC ○ ○ 97.9 0.18 334 Example 80 LC ○ ○ 97.5 0.21

The composition of the liquid crystal composition used for the liquid crystal display element of the said Example is shown next. In addition, these physical properties are shown in Table 18.

Composition (LA)

Liquid Crystal Composition (LB)

Liquid Crystal Composition (LC)

Liquid Crystal Composition (LD)

Liquid crystal composition (LE)

Liquid Crystal Composition (FB01)

The photosensitive resin composition of this invention is excellent in solvent resistance, heat resistance, and rubbing resistance, has the characteristic which does not produce the liquid-crystal orientation defect, and does not reduce voltage retention and residual DC, but it is highly sensitive and the development residue ( There is no scum), and thus the liquid crystal display spacer having excellent developability and solvent resistance is formed.

Moreover, the liquid crystal display element of this invention which has a spacer formed using the photosensitive resin composition of this invention as material is excellent in rubbing resistance, and does not affect electrical characteristics, such as an afterimage phenomenon of a liquid crystal, voltage retention, and also The aperture ratio and contrast are excellent, the mechanical strength is high, and the layer thickness of the liquid crystal layer is uniform.

Claims (16)

Alkali-soluble resin [A], the compound [B] which has ethylenically unsaturated bond, the organic peroxide photoinitiator [C] which has a benzophenone structure, and the photosensitizer which has a 4,4'-bis (dialkylamino) benzophenone structure [D] ], The photosensitive resin composition characterized by including the. The photosensitive resin composition of Claim 1 whose alkali-soluble resin [A] is a copolymer of unsaturated carboxylic monomer (a-1) and other radically polymerizable monomer. The radically polymerizable monomer (a-2) of the formula (1) or the radically polymerizable monomer (a-2) and the radically polymerizable monomer (a-3) of the formula (1). Radical polymerizable monomers other than (a-1) and (a-2)]. Formula 1 Where R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, n is an integer of 0-5. The photosensitive resin composition of claim 3, wherein n is 1 or 2 in the general formula (1). The photosensitive resin composition according to claim 3 or 4, wherein in Formula 1, R ₁ and R ₂ are hydrogen atoms. The photosensitive resin composition of Claim 2 whose other radically polymerizable monomer is a radically polymerizable monomer (a-3). The photosensitive resin composition of any one of Claims 1-6 whose organic peroxide photoinitiator [C] which has a benzophenone structure is a compound of General formula (2). Formula 2 Where R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 13 carbon atoms, X ₁ and X ₂ are each independently —O—, —OO—, or —NH—. The photosensitive resin composition of claim 7, wherein in Formula 2, X ₁ and X ₂ are both -O-. The photosensitive resin composition of any one of Claims 1-8 whose compound [B] is a compound which has 3-6 ethylenically unsaturated bonds. The photosensitive resin composition of any one of Claims 1-9 whose ethylenically unsaturated bond of compound [B] is acryloyl group or methacryloyl group. The photosensitive resin composition of any one of Claims 1-10 which further added the alkali insoluble vinyl polymer [A _IS ] which has an epoxy group. The polymer or copolymer of the radically polymerizable monomer (a-4) having an epoxy group or the radically polymerizable monomer of the monomer (a-4) according to claim 11, wherein the alkali insoluble vinyl polymer [A _IS ] having an epoxy group is used. Photosensitive resin composition which is a copolymer with (a-5). The film formed using the photosensitive resin composition of any one of Claims 1-12. The spacer for liquid crystal display elements formed using the photosensitive resin composition of any one of Claims 1-12. The liquid crystal display device spacer according to claim 14, wherein the photosensitive resin composition is thermally cured after being patterned by plate printing. A liquid crystal display element having a spacer as claimed in claim 14 or 15.