JP2003302642A - Radiation sensitive resin composition to be used for formation of spacer by ink jet method, spacer and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a spacer composition optimized for the manufacture of a spacer by a low-cost ink jet method and to provide a spacer formed from the composition and a liquid crystal display element equipped with the spacer. <P>SOLUTION: The composition comprises: [A] a copolymer of (a1) an unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, (a2) an epoxy group-containing unsaturated compound and (a3) an olefin unsaturated compound except for compounds of (a1) and (a2); [B] a polymerizable compound having an ethylenic unsaturated bond; [C] a radiation sensitive polymerization initiator; and [D] a solvent having ≥180°C boiling point at normal pressure. The spacer is formed from the above composition, and the liquid crystal display element has the above spacer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition used for forming a spacer by an inkjet method, a spacer formed from the same, and a liquid crystal display device having the spacer. For more details,
Radiation-sensitive resin composition suitable for forming a spacer for a liquid crystal display element on a substrate such as glass or resin by an inkjet method, a spacer formed from the resin composition,
And a liquid crystal display device having the spacer thereof.

[0002]

2. Description of the Related Art Conventionally, a liquid crystal panel has glass beads having a predetermined particle diameter in order to keep a distance between two substrates constant,
Spacer particles such as plastic beads have been used. Since these spacer particles are randomly dispersed on the glass substrate, if the spacer is present in the effective pixel portion, there is a problem that the spacer is reflected or incident light is scattered and the contrast of the liquid crystal panel is lowered. there were. In order to solve these problems, a method of forming a spacer by photolithography has been used. According to this method, the radiation-sensitive resin composition can be applied to a substrate, irradiated with radiation such as ultraviolet rays through a predetermined mask, and then developed to form dot-shaped or stripe-shaped spacers. According to this, it is known that the spacer can be formed in a place other than the effective pixel portion, and the above problem can be solved.

As a method for forming such a spacer, conventionally, a radiation-sensitive resin composition is applied onto the surface of a substrate such as a color filter by a spray method, a roll coating method, a spin coating method, a bar coating method or the like. Then, it is known that a solvent is removed by prebaking to form a coating film, and then a heat treatment is performed to obtain a uniform film, and a desired spacer is formed by photolithography. However, in these methods, a large amount of the resin composition is used for stable coating, which is more than the amount of the resin composition required for forming the spacer. Therefore, there has been a problem that the resin composition is wasted a lot, resulting in high cost. On the other hand, JP-A-5
No. 9-75205, JP-A No. 61-245106, JP-A No. 63-235901, etc., an inkjet color filter having a step of forming a colored layer of a color filter using an inkjet head. Is disclosed, and in this method, it is easy to control the position at which the droplets of the resin composition for a color filter are ejected, and the waste of the resin composition is reduced, so that the manufacturing cost can be reduced. is there. However, these publications do not give sufficient consideration to the composition for spacers, which is suitable for the inkjet system.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is to provide a spacer composition optimized for the production of a spacer by a low-cost inkjet method, and Providing a formed spacer. Another object of the present invention is to provide a liquid crystal display device including the spacer as described above.

[0005]

According to the present invention, the above-mentioned problems are [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) epoxy group-containing unsaturated compound, and (A3) The above (a1) and (a
Copolymers of olefinic unsaturated compounds other than 2) (hereinafter sometimes referred to as "copolymer [A]"), [B].
A photosensitive composition used for forming a spacer by an inkjet method, which comprises a polymerizable compound having an ethylenically unsaturated bond, [C] a radiation-sensitive polymerization initiator, and [D] a solvent having a boiling point of 180 ° C. or higher at normal pressure. This is achieved by the radiation-sensitive resin composition.

Further, according to the present invention, the above problems are secondly achieved by a spacer formed from the radiation sensitive resin composition, and thirdly achieved by a liquid crystal display device having the spacer. Hereinafter, each component of the radiation-sensitive resin composition for a spacer of the present invention will be described in detail. In the present invention, the term "radiation" is used as a concept including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays, synchrotron radiation, proton beam rays and the like.

Copolymer [A] The copolymer [A] comprises (a1) an unsaturated carboxylic acid and /
Or unsaturated carboxylic acid anhydride (hereinafter referred to as "compound (a
1) ”. ), (A2) an epoxy group-containing unsaturated compound (hereinafter sometimes referred to as “compound (a2)”), and (a3) the above (a1) and (a).
It can be produced by radical polymerization of an olefinic unsaturated compound other than 2) (hereinafter sometimes referred to as "compound (a3)") in a solvent in the presence of a polymerization initiator. The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a1), preferably 5 units.
˜50% by weight, particularly preferably 10 to 40% by weight. When this structural unit is less than 5% by weight, the compressive strength, heat resistance and chemical resistance of the obtained spacer tend to be lowered. On the other hand, if it exceeds 50% by weight, the storage stability of the radiation-sensitive resin composition may decrease.

Examples of the compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;
And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids. Of these, acrylic acid,
Methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity and easy availability. These may be used alone or in combination.

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a2), preferably 1
0 to 70% by weight, particularly preferably 20 to 60% by weight. When the content of this structural unit is less than 10% by weight, the compressive strength, heat resistance and chemical resistance of the resulting spacer tend to be lowered, while when it exceeds 70% by weight, the storage stability of the radiation-sensitive resin composition tends to be low. It tends to decrease.

Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic acid-3,4. -Epoxybutyl, methacrylic acid-3,4-
Epoxy butyl, 6,7-epoxy heptyl acrylate, 6,7-epoxy heptyl methacrylate, α-ethyl 6,7-epoxy heptyl acrylate, β-methyl glycidyl methacrylate, β-ethyl methacrylate Examples thereof include glycidyl, β-propylglycidyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like. Of these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether,
m-Vinylbenzyl glycidyl ether, p-vinyl benzyl glycidyl ether, methacrylic acid-β-methyl glycidyl ether and the like are preferably used from the viewpoint of increasing the copolymerization reactivity and the strength of the resulting spacer. These may be used alone or in combination.

The copolymer [A] contains the structural unit derived from the compound (a3) in an amount of preferably 10 to 80% by weight, particularly preferably 20 to 60% by weight. If this structural unit is less than 10% by weight, the storage stability may decrease, while if it exceeds 80% by weight, the copolymer [A] becomes difficult to dissolve in an aqueous alkaline solution. Examples of the compound (a3) include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec
-Methacrylic acid alkyl esters such as butyl methacrylate and t-butyl methacrylate; acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.
Cyclic alkyl methacrylates such as 1.0 ^2,6 ] decan-8-yl methacrylate (commonly known in the art as dicyclopentanyl methacrylate), dicyclopentanyloxyethyl methacrylate, and isobornyl methacrylate. Ester; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (commonly known in the art as dicyclopentanyl acrylate), diester Acrylic acid cyclic alkyl esters such as cyclopentanyloxyethyl acrylate and isobornyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Phenyl acrylate and benzyl acrylate Acrylic acid aryl ester; Dicarboxylic acid diester such as diethyl maleate, diethyl fumarate, diethyl itaconic acid; Hydroxyalkyl ester such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; and styrene, α-methylstyrene, m-methyl Styrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,
3-dimethyl-1,3-butadiene, phenylmaleimide, cyclohexylmaleimide, benzylmaleimide,
N-succinimidyl-3-maleimidobenzoate,
N-succinimidyl-4-maleimidobutyrate, N
-Succinimidyl-6-maleimidocaproate, N
-Succinimidyl-3-maleimidopropionate,
Examples thereof include N- (9-acridinyl) maleimide.

Of these, styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-
Methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene and the like are preferable from the viewpoint of copolymerization reactivity. These may be used alone or in combination.

Preferred specific examples of the copolymer [A] include, for example, acrylic acid / glycidyl acrylate / styrene copolymer, acrylic acid / glycidyl methacrylate /
Styrene copolymer, methacrylic acid / glycidyl acrylate / styrene copolymer, methacrylic acid / glycidyl methacrylate / styrene copolymer, acrylic acid / glycidyl acrylate / styrene / tricyclo [5.2.1.0 ^2,6 ]
Decan-8-yl methacrylate copolymer, acrylic acid / glycidyl methacrylate / styrene / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate copolymer, methacrylic acid / glycidyl acrylate / styrene /Tricyclo[5.2.1.0 ^2,6 ] decan-8-yl methacrylate copolymer, methacrylic acid / glycidyl methacrylate / styrene / tricyclo [5.2.1.1.
0 ^{2, 6]} decan-8-yl methacrylate copolymer,
Acrylic acid / glycidyl acrylate / styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / 1,3-butadiene copolymer, acrylic acid / glycidyl methacrylate / styrene / tricyclo [5 .2.
1.0 ^2,6 ] Decan-8-yl methacrylate / 1,3
-Butadiene copolymer, methacrylic acid / glycidyl acrylate / styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / 1,3-butadiene copolymer, methacrylic acid / glycidyl methacrylate / styrene / tricyclo [5.2.1.0 ^{2, 6]} decan-8-yl methacrylate / 1,3-butadiene copolymers, acrylic acid / glycidyl acrylate / tricyclo [5.2.
1.0 ^2,6 ] Decan-8-yl methacrylate / 1,3
-Butadiene copolymer, acrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / 1,3-butadiene copolymer, methacrylic acid / glycidyl acrylate / tricyclo [5.
2.1.0 ^2,6 ] Decan-8-yl methacrylate /
1,3-butadiene copolymer, methacrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / 1,3-butadiene copolymer, acrylic acid / acrylic acid Glycidyl / t-butyl methacrylate / 1,3-butadiene copolymer, acrylic acid / glycidyl methacrylate / t-butyl methacrylate / 1,3-butadiene copolymer, methacrylic acid / glycidyl acrylate / t-butyl methacrylate / 1 ，
Examples thereof include 3-butadiene copolymer and methacrylic acid / glycidyl methacrylate / t-butyl methacrylate / 1,3-butadiene copolymer.

Specific examples of the solvent used for producing the copolymer [A] include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like. Glycol ethers; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether; propylene glycol methyl ether, Propylene glycol ethyl ether, pro Glycol propyl ether,
Propylene glycol monoalkyl ethers such as propylene glycol butyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate , Propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and other propylene glycol alkyl ether acetates; aromatic hydrocarbons such as toluene and xylene;

Methyl ethyl ketone, cyclohexanone,
Ketones such as 4-hydroxy-4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate,
Methyl 2-hydroxy-2-methylpropionate, 2-
Ethyl hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxy Propyl propionate, butyl 3-hydroxypropionate, 2-
Methyl hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl 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, butoxyacetate Butyl, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate , Butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate,
Propyl 2-butoxypropionate, Butyl 2-butoxypropionate, Methyl 3-methoxypropionate, 3
-Ethyl methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-
Methyl ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Butyl propionate, methyl 3-butoxypropionate, 3-
Examples thereof include esters such as ethyl butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

As the polymerization initiator used for producing the copolymer [A], those generally known as radical polymerization initiators can be used, for example, 2,2'-azobisisobutyronitrile, Azo compounds such as 2,2'-azobis- (2,4-dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t- Butyl peroxypivalate, organic peroxides such as 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox type initiator.

The copolymer [A] used in the present invention has a polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) of usually 2 × 10 ^{3 to} 5 × 10 ⁵ , preferably 5 ×.
It is desirable that it is 10 ³ to 1 × 10 ⁵ . Mw is 2 × 1
When it is less than 0 ³ , the resulting spacer has compressive strength,
The heat resistance tends to decrease. On the other hand, when it exceeds 5 × 10 ⁵ , the developability tends to decrease in the spacer forming step.

[B] Polymerizable compound having an ethylenically unsaturated bond [B] A polymerizable compound having an ethylenically unsaturated bond (hereinafter, may be referred to as "polymerizable compound [B]"). As (), a bifunctional or trifunctional or higher functional (meth) acrylate is preferably used. Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples thereof include tetraethylene glycol di (meth) acrylate and bisphenoxyethanol full orange acrylate. Examples of the commercially available products include Aronix M-210 and M-24.
0, the same M-6200 (above, manufactured by Toagosei Co., Ltd.), KA
YARAD HDDA, HX-220, R-604
(Nippon Kayaku Co., Ltd.), Viscoat 260, 3
12, 335 HP (Osaka Organic Chemical Industry Co., Ltd.)
Manufactured) and the like.

Examples of the trifunctional or higher functional (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. Examples thereof include (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Examples of commercially available products include Aronix M-309, M-400, and M-40.
2, same M-405, same M-450, same M-7100, same M-8030, same M-8060, same M-1310, same T
O-1450, M-1600, M-1960, M
-8100, M-8530, M-8560, M-
9050 (all manufactured by Toagosei Co., Ltd.), KAYARAD
TMPTA, DPHA, DPCA-20, DP
CA-30, DPCA-60, DPCA-120,
MAX-3510 (above, manufactured by Nippon Kayaku Co., Ltd.), Viscoat 295, 300, 360, GPT, 3P.
A, 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like. These bifunctional or trifunctional or higher functional (meth) acrylates may be used alone or in combination. The radiation-sensitive resin composition of the present invention contains the polymerizable compound [B] based on 100 parts by weight of the copolymer [A].
Preferably 30 to 200 parts by weight, more preferably 50 to
Contains 150 parts by weight. When the amount of the polymerizable compound [B] is less than 30 parts by weight, the resulting spacer tends to be reduced in film thickness and strength, and when it exceeds 200 parts by weight, the adhesiveness of the obtained spacer may be insufficient.

[C] Radiation-sensitive polymerization initiator [C] Radiation-sensitive polymerization initiator used in the present invention (hereinafter,
It may be referred to as "polymerization initiator [C]". )as,
For example, a radiation sensitive radical polymerization initiator can be mentioned. Examples of such radiation-sensitive radical polymerization initiators include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2 , 4-Diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-
Benzophenones such as bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; acetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-phenylacetophenone , P-methoxyacetophenone, 2-methyl [4-
(Methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-
Acetophenones such as (4-morpholinophenyl) -butan-1-one; quinones such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-triazine, etc. Halogen compounds; 2,4,6
-Trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4
-Arylphosphine oxides such as trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide; and peroxides such as di-t-butyl peroxide.

Commercially available products of these polymerization initiators include, for example, IRGACURE-184, 369, 500,
651, 907, 1700, 819, 12
4, same 1000, same 2959, same 149, same 1800,
1850, Darocur-1173, 1116,
2959, 1664, 4043 (all manufactured by Ciba Specialty Chemicals), KAYACURE-
DETX, MBP, DMBI, EP
A, the same OA (above, Nippon Kayaku Co., Ltd.), LUCIR
INTPO (manufactured by BASF Co. LTD), VIC
URE-10, 55 (above, STAUFER C
o.LTD), TRIGONAL P1 (AKZO
Co. LTD), SANDORAY 1000 (S
ANDOZ Co. LTD), DEAP (APJO
HN Co. LTD), QUANTACURE-P
DO, ITX, EPD (above, WARD BL
EKINSOP Co. LTD) and the like.

Preferred examples of such a radiation-sensitive radical polymerization initiator include benzophenones and acetophenones, of which 2,4-diethylthioxanthone and 2-methyl [4-
(Methylthio) phenyl] -2-morpholino-1-propanone, and 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butan-1-one is preferred.

In the radiation-sensitive resin composition of the present invention, the polymerization initiator [C] is added to 100 parts by weight of the copolymer [A].
The content is preferably 1 to 50 parts by weight, more preferably 5 to 35 parts by weight. The amount of the polymerization initiator [C] is 1
If the amount is less than 50 parts by weight, the resulting film of the spacer tends to be reduced in film thickness and strength, and if the amount exceeds 50 parts by weight, the eluate in the liquid crystal tends to affect the voltage holding ratio. It is also possible to obtain a highly sensitive radiation-sensitive resin composition with little deactivation by oxygen by using these polymerization initiators [C] and a radiation-sensitizer together.

[D] Solvent having a boiling point of 180 ° C. or higher at normal pressure The solvent in the present invention is a solvent having a boiling point of 180 ° C. or higher (hereinafter, simply referred to as “boiling point”) at normal pressure (1 atm). High boiling point solvent "[D]). The boiling point of the high boiling point solvent is preferably 200 ° C. or higher. Further, the upper limit of the boiling point of the high boiling point solvent, as long as the spacer can be manufactured by an inkjet method from the radiation sensitive resin composition for inkjet method of the present invention,
Although not particularly limited, from the viewpoint of operability in the resin composition preparation step and the spacer manufacturing step, the boiling point is 290 ° C. or lower, preferably 280 ° C. or lower, and is relatively room temperature (20 ° C.). A high boiling solvent that is a low viscosity liquid is desirable. Therefore, the preferable boiling range of the high boiling point solvent in the present invention is specifically 180 to 290.
C., more preferably 200 to 280.degree.

As the high boiling point solvent, for example, a compound of the formula R ¹ -O (CH
₂ CH ₂ O) ₂ -R ² (provided that R ¹ and R ² independently have 2 carbon atoms
10 represents an alkyl group. ) A diethylene glycol dialkyl ether solvent represented by the formula; Formula R ³ -O (CH ₂ CH ₂ O)
₃ -R ⁴ (provided that R ³ and R ⁴ independently of each other have 1 to 10 carbon atoms).
Is an alkyl group. ) A triethylene glycol dialkyl ether solvent represented by the formula: R ⁵ -O (CH ₂ CH ₂ O) _i -R ⁶
(However, R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms, and i is an integer of 2 to 30.) A polyethylene glycol dialkyl ether solvent represented by the formula R ⁷ — A propylene glycol dialkyl ether solvent represented by OCH (CH ₃ ) CH ₂ OR ⁸ (wherein R ⁷ and R ⁸ independently represent an alkyl group having 2 to 10 carbon atoms);

Ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, etc. ethylene glycol monoalkyl ethers; ethylene glycol monobutyl ether acetate, etc. ethylene glycol monoalkyl ether acetates; diethylene glycol monomethyl ether, Diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, die Diethylene glycol monoalkyl ether acetates such as len glycol mono-n-butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol butyl ether acetate; Others such as ethylene glycol monophenyl ether acetate, diethylene glycol diethyl ether, benzyl ethyl ether, dihexyl ether Ethers of

Alcohols such as 1-octanol, 1-nonanol and benzyl alcohol; ketones such as acetonylacetone and isophorone; carboxylic acids such as caproic acid and caprylic acid; butyl lactate, ethyl benzoate, n-butyl benzoate. , Diethyl oxalate, diethyl maleate, di-n-butyl maleate, glycerin triacetate, di-n-butyl fumarate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-i-phthalate Examples thereof include ester solvents such as propyl, di-n-butyl phthalate, i-amyl salicylate, γ-butyrolactone, ethylene carbonate and propylene carbonate.

Specific examples of preferred high boiling point solvents in the present invention include ethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol, propylene glycol butyl ether acetate, diethylene glycol di-n. -Butyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, propylene glycol di-n-butyl ether, butyl lactate and the like are preferable. The high boiling point solvents may be used alone or in admixture of two or more.

The amount of the high boiling point solvent used is such that the copolymer [A] 1
It is usually 10 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, and more preferably 100 to 2,000 parts by weight with respect to 00 parts by weight. When the amount used is in this range, it is possible to obtain a composition having excellent controllability of the drying speed of the discharged resin composition and excellent coating properties.

In the present invention, the following effects can be obtained by using the high boiling point solvent. That is, when the spacer is formed by the inkjet method, the composition for spacer is discharged to remove the solvent, and then heated to form the spacer application film, but the evaporation rate of the high boiling point solvent at this time is low, Since the discharged resin composition does not change abruptly during solvent removal or heating, the work margin at the time of forming the spacer is improved. When the spacer is formed by the inkjet method, the composition for the spacer gradually becomes viscous due to the evaporation of the solvent, but when the boiling point of the solvent is low, it becomes difficult to control the viscosity change, and it is difficult to control the initial spacer formation process. At the end of the period, the degree of change of the resin composition discharged onto the substrate increases, which hinders the formation of spacers. Can be controlled to a desired value, and a desired spacer can be easily formed. Since it is possible to prevent clogging of the ink jet head portion that ejects the composition for spacers due to dryness of the composition, and also to prevent flight bending when ejecting the composition, and to ensure good straightness, it is possible to use spacers The utilization efficiency of the composition and the cleaning efficiency of the manufacturing apparatus are improved.

In the present invention, the boiling point is 180 ° C.
A solvent of less than (hereinafter, referred to as “low-boiling point solvent”) can be used in combination with the high-boiling point solvent. Examples of such a low boiling point solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate and the like. Ethylene glycol alkyl ether acetates; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, etc. ethylene glycol monoalkyl ether acetates; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Propylene glycol Alkyl ether acetates; diethylene glycol dimethyl ether, other ethers such as tetrahydrofuran;

Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; propylene glycol methyl ether acetate,
Propylene glycol alkyl ether acetates such as propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate;

Alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4
-Methyl-2-pentanone, 2-heptanone, 3-heptanone, methyl isoamyl ketone and other ketones; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, methyl acetoacetate , Ethyl acetoacetate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate,
Methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 2-hydroxy-3-methylbutanoic acid Methyl,
Methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, methyl 2-methoxypropionate , Ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate,
Methyl 3-propoxypropionate, ethyl 3-propoxypropionate, methyl 3-butoxypropionate,
Esters such as ethyl 3-butoxypropionate may be mentioned.

Of these, diethylene glycols,
Propylene glycol monoalkyl ethers, propylene glycol alkyl acetates, and esters are preferable, and particularly diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxypropionic acid. Methyl, ethyl 3-ethoxypropionate, methyl lactate,
Ethyl lactate is preferred.

These low boiling point solvents may be used alone or in admixture of two or more. The use ratio of the low boiling point solvent is based on the total of the high boiling point solvent and the low boiling point solvent,
Usually, it is 50% by weight or less, preferably 30% by weight or less. In this case, if the proportion of the low boiling point solvent used exceeds 50% by weight, the intended effect of using the high boiling point solvent may be impaired.

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention is prepared by uniformly mixing the above components. Usually, the radiation-sensitive resin composition of the present invention is dissolved in an appropriate solvent and used in a solution state. The radiation-sensitive resin composition of the present invention,
Other optional additives other than the above may be contained as necessary within the range not impairing the object of the present invention. Examples of such other optional additives include [E] adhesion aid, [F]
Examples thereof include a surfactant, [G] a compound that generates a radical by heat, and [H] a compound represented by the following general formula (1) or (2).

The above-mentioned [E] adhesion aid can be used to improve the adhesion between the formed spacer and the substrate. As such an adhesion aid, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group. Specifically, trimethoxysilylbenzoic acid,
γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,
γ-isocyanatopropyltriethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

Such an adhesion aid is a copolymer [A] 1.
It is preferably used in an amount of 20 parts by weight or less, more preferably 0.5 to 10 parts by weight, based on 00 parts by weight. When the amount of the adhesion aid exceeds 20 parts by weight, the undeveloped portion is likely to occur.

The above-mentioned [F] surfactant can be added to improve the coating property of the composition. As such a [F] surfactant, a fluorine-based surfactant and a silicone-based surfactant can be preferably used.
As the fluorine-based surfactant, a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain and side chain can be preferably used, and specific examples thereof include 1,1,2 , 2-Tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)
Ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,
2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,
2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8, 8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphonate, sodium fluoroalkylcarboxylate, fluoroalkyl Polyoxyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate , It may be mentioned fluorine-based alkyl esters.

Examples of commercially available products thereof include BM-1
000, BM-1100 (above, manufactured by BM CHEMIE), MegaFac F142D, the same F172, the same F17.
3, Same F183, Same F178, Same F191, Same F47
1, the same F476 (above, Dainippon Ink and Chemicals, Inc.)
Manufactured), Florard FC 170C, FC-171, FC
-430, FC-431 (above, Sumitomo 3M Ltd.)
Manufactured), Surflon S-112, S-113, S-1
31, same S-141, same S-145, same S-382, same SC-101, same SC-102, same SC-103, same S
C-104, SC-105, SC-106 (above,
Asahi Glass Co., Ltd., F-top EF301, 303,
352 (above, manufactured by Shin-Akita Kasei Co., Ltd.), Futergent FT-100, FT-110, FT-140A,
FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300,
The same FT-310, the same FT-400S (above, Neos Co., Ltd. make) etc. can be mentioned. As the silicone-based surfactant, for example, Toray Silicone DC3P
A, same DC7PA, same SH11PA, same SH21PA,
SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, Toray Dow Corning Silicone Co., Ltd.) Made), T
SF-4440, TSF-4300, TSF-444
5, TSF-4446, TSF-4460, TSF-4
452 (above, manufactured by Toshiba Silicone Co., Ltd.) and the like are commercially available.

In addition, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Ethylene aryl ethers; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.)
Manufactured), (meth) acrylic acid type copolymer polyflow No.
57, 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and the like.

These [F] surfactants are used in an amount of preferably 1.0 part by weight or less, more preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the copolymer [A]. . When the amount of the surfactant exceeds 1.0 part by weight, unevenness of the film is likely to occur.

The compound [G] that generates a radical by heat (hereinafter, may be referred to as "thermal radical polymerization initiator [G]") is fired at a low temperature when a spacer is formed on a resin substrate. If necessary, it may be added to improve the low temperature curability. Examples of such thermal radical polymerization initiator [G] include 2,2′-
Azobisisobutyronitrile, 2,2'-azobis-2
-Methylbutyronitrile, 2,2'-azobis (2,4-
Dimethylvaleronitrile), 2,2'-azobis (4-
Methoxy-2,4-dimethylvaleronitrile), 1,1 '
-Azobis-1-cyclohexylnitrile, dimethyl-
Azo compounds such as 2,2′-azobisisobutyrate, 4,4′-azobis-4-cyanovaleric acid and 1,1′-azobis (1-acetoxy-1-phenylethane); benzoyl peroxide, lauroyl per Oxide, te
rt-Butyl peroxide, 1,1′-bis (ter
Organic peroxides such as t-butylperoxy) cyclohexane can be mentioned. Among these, preferred are azo compounds, and of these, 2,2'-azobisisobutyronitrile and 1,1'-azobis-1-cyclohexylnitrile are particularly preferred.

When these thermal radical polymerization initiators [G] are used, the addition amount thereof is 20 parts by weight or less, preferably 0.5 to 20 parts, relative to 100 parts by weight of the copolymer [A].
It is a part by weight, more preferably 2 to 10 parts by weight.
When the amount used is in this range, it is possible to obtain a composition having an excellent balance between the compressive strength and heat resistance of the resulting spacer and the surface smoothness of the coating film.

The component [H] is a compound represented by the following general formula (1) or (2).

[0046]

[Chemical 1]

(In the formula, R ^{9 to} R ¹⁴ may be the same or different and each represents a hydrogen atom or a group —CH ₂ OR, and R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

[0048]

[Chemical 2]

(In the formula, R ^{15 to} R ¹⁸ may be the same or different and each is a hydrogen atom or a group —CH ₂ O.
R'indicates a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ) Examples of such compounds include hexamethylolmelamine, hexabutyrolmelamine, partially methylolated melamine and its alkylated products, tetramethylolbenzoguanamine, partially methylolated benzoguanamine and its alkylated products, and the like. Commercially available products of such compounds include, for example, Cymel 300, 3
01, 303, 370, 325, 327, 701, 26
6, 267, 238, 1141, 272, 202, 11
56, 1158, 1123, 1170, 1174, UF
R65, 300 (above, Mitsui Cyanamide Co., Ltd.
Manufactured by Nikarac Mx-750, -032, -706,
-708, -40, -31, Nikarac Ms-11, Nikarac Mw-30 (above, Sanwa Chemical Co., Ltd. product)
And the like can be preferably used. These [H]
The amount of the component added is preferably 50 parts by weight or less, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the copolymer [A].
0 parts by weight, particularly preferably 5 to 30 parts by weight. When the amount used is in this range, a composition having an excellent balance between the compressive strength and heat resistance of the resulting spacer and the developability in the spacer forming step can be obtained. The composition solution prepared as described above can be used after being filtered using a Millipore filter having a pore size of about 0.5 μm.

Formation of Spacer Next, a method for forming the spacer of the present invention by using the radiation-sensitive resin composition of the present invention will be described. The radiation-sensitive resin composition of the present invention is applied to the surface of a substrate by an inkjet device, and then the applied surface is heated (prebaked) to form a coating film. As the substrate that can be used, there are substrates made of glass, quartz, silicon, resin or the like. As the resin substrate, a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and polyimide can be used. A NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG Company, USA), indium oxide-tin oxide (In ₂ O ₃ —SnO)
_The ITO film made of ₂ ) or the like may be formed on a substrate provided as a transparent conductive film on one surface of the substrate. The pre-baking conditions vary depending on the type of each component, the mixing ratio, etc.,
It is usually at 70 to 120 ° C. for about 1 to 15 minutes.

Next, the coating film formed as described above is irradiated with radiation through a predetermined pattern mask and further developed to remove unnecessary portions to form a predetermined pattern. As the radiation used, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, but the wavelength is 190 to 4
Radiation in the range of 50 nm is preferred, especially 360 n
m radiation (ultraviolet light) is preferred. The exposure dose is usually 100
To 10,000 J / m ² , preferably 1,500
˜3,000 J / m ² . The developer used in the developing step is an aqueous alkaline solution, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; ethylamine, n-propylamine, and the like. Primary amines; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine; dimethylethanolamine, methyldiethanolamine, triethanolamine and the like 3
Primary amines; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5- Cyclic tertiary amines such as nonene;
Aromatic tertiary amines such as pyridine, collidine, lutidine, and quinoline; aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide can be used. Further, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant to the above alkaline aqueous solution can be used as a developing solution. The developing method may be any of a puddle method, a dipping method, a shower method and the like, and the developing time is usually 10 to 180 seconds.

After development, washing with running water is carried out for 30 to 90 seconds,
Furthermore, by air drying with compressed air or compressed nitrogen,
The desired pattern is formed. The heat treatment of the formed pattern can be performed by a heating device such as a hot plate or an oven. The processing temperature is usually 1
The temperature is preferably about 50 to 250 ° C. For example, a desired spacer can be obtained by performing a heat treatment (post-baking) on a hot plate for 5 to 30 minutes and in an oven for 30 to 180 minutes. In particular, when a thermal radical polymerization initiator [G] or [H] component is added, 100 to 1
It is possible to obtain a spacer excellent in various properties such as strength, rubbing resistance, and adhesion to a substrate even at a low temperature of about 50 ° C.

Liquid Crystal Display Element Next, the liquid crystal display element of the present invention will be described. The liquid crystal display element of the present invention has the spacer formed as described above. The liquid crystal element may have any suitable structure. For example, as shown in FIG. 1, the color filter layer and the spacer of the present invention are formed on a glass substrate, and they are opposed to each other with an alignment film and a liquid crystal layer interposed therebetween. The structure may include an alignment film, a transparent electrode facing the alignment film, and a glass substrate facing the alignment film. Further, if necessary, a protective film may be formed on the polarizing plate or the color filter layer. Further, as shown in FIG. 2, a color filter layer and a spacer are formed on a glass substrate and faced with a TFT array substrate via an alignment film and a liquid crystal layer, whereby a TN-TFT type liquid crystal display element can be obtained. Here, if necessary, a protective film may be formed on the polarizing plate or the color filter.

[0054]

EXAMPLES Synthesis Example 1 A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 20 parts by weight of styrene, 17 parts by weight of methacrylic acid, 18 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and 45 parts by weight of glycidyl methacrylate were charged, and the atmosphere was replaced with nitrogen. The stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The solid content concentration of the obtained polymer solution was 28.
4% by weight, and the weight average molecular weight of the polymer is 16,0.
It was 00 (the weight average molecular weight is a polystyrene-equivalent molecular weight measured using GPC (gel permeation chromatography) HLC-8020 (manufactured by Tosoh Corporation)).

Synthesis Example 2 A flask equipped with a cooling tube and a stirrer was charged with 4 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, tricyclo [5.2.1.0 ^2,6 ] decane-
After 34 parts by weight of 8-yl methacrylate and 40 parts by weight of glycidyl methacrylate were charged and the atmosphere was replaced with nitrogen, 5 parts by weight of 1,3-butadiene was further charged and stirring was gently started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-2]. The solid content concentration of the obtained polymer solution is 28.6% by weight.
And the weight average molecular weight of the polymer was 15,000.

Example 1 Preparation of Radiation-Sensitive Resin Composition Solution containing the copolymer [A-1] obtained in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer [A-1]) ) And KAYARADPDPHA as the polymerizable compound [B-1]
(Manufactured by Nippon Kayaku Co., Ltd.) and 100 parts by weight of a polymerization initiator [C
-1] as 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name "IRGACURE 907" manufactured by Ciba Specialty Chemicals) 25 parts by weight, high boiling solvent 700 parts by weight of diethylene glycol monobutyl ether acetate as [D-1], 5 parts by weight of γ-glycidoxypropyltrimethoxysilane as [E] adhesion aid, and SH-28PA (Toray Silicone (Toray Silicone ( stock)
0.05 parts by weight, and the mixture is diluted and dissolved with diethylene glycol dimethyl ether so that the solid content concentration becomes 20% by weight, and then filtered through a Millipore filter having a pore size of 0.5 μm to obtain a radiation-sensitive resin composition. A solution (1) of was prepared.

Formation of Spacer The above composition solution was applied onto a glass substrate using an inkjet device, and then prebaked at 90 ° C. for 3 minutes on a hot plate to form a coating film having a thickness of 5.0 μm. The coating film obtained above was irradiated with ultraviolet rays having an intensity at 365 nm of 250 W / m ² for 10 seconds through a mask having a remaining pattern of 10 μm square. Then sodium carbonate 0.
After developing with a 5% by weight aqueous solution at 25 ° C. for 60 seconds, it was rinsed with pure water for 1 minute. Further, in an oven at 220 ° C for 6
The spacer was formed by heating for 0 minutes.

Evaluation of Resolution In the pattern obtained above, the case where the remaining pattern could be resolved was defined as good, and the case where it could not be resolved was defined as poor. The results are shown in Table 1. Evaluation of Pattern Cross-sectional Shape As a result of observing the cross-sectional shape of the pattern with a scanning electron microscope, Table 1 shows which of the shapes A to C shown in FIG. When the pattern edge is formed in a forward tapered shape or a vertical shape as in A or B, the pattern shape can be said to be good. If the taper has an inverse taper like C, the adhesiveness and the like become a problem, so that it is evaluated as defective.

Evaluation of compressive strength The compressive strength of the spacers obtained above was evaluated using a micro compression tester (MCTM-200, manufactured by Shimadzu Corporation). The amount of deformation when a load of 10 mN was applied was measured with a plane indenter having a diameter of 50 μm (measurement temperature: 23
C). When this value is 0.5 μm or less, the compressive strength is good. The results are shown in Table 1. Evaluation of rubbing resistance The substrate obtained above was treated with AL304 as a liquid crystal aligning agent.
6 (manufactured by JSR Co., Ltd.) was applied with a printing machine for coating liquid crystal alignment film, heated at 180 ° C. for 1 hour to remove the solvent, and a coating film of the alignment agent having a dry film thickness of 0.05 μm was formed. Formed. The number of rotations of the roll was 50 by a rubbing machine having a roll in which a nylon cloth was wound around this coating film.
The rubbing treatment was performed at 0 rpm and a stage moving speed of 1 cm / sec. Table 1 shows whether the spacer pattern was scraped or peeled at this time.

Evaluation of Adhesiveness A cured film for adhesiveness evaluation was formed in the same manner as above except that a pattern mask was not used, and an adhesiveness test was conducted. The test method is JIS K-5400 (1900)
Of the 8.5 adhesion tests, the cross-cut tape method of 8.5 · 2 was followed. At that time, Table 1 shows the number of grids remaining.

Evaluation of Inkjet Coating Property In the same manner as described above, the above composition was coated on a glass substrate so as to have a film thickness of 5.0 μm, and then on a hot plate at 90 ° C. for 3 minutes. It was prebaked to form a coating film. Without using a pattern mask,
1 UV ray with an intensity of 250 W / m ² at 365 nm
It was irradiated for 0 seconds to prepare a substrate for evaluation. The unevenness of the surface of this coating film was measured with a contact-type film thickness measuring device α-step (manufactured by Tencor Japan Co., Ltd.) to measure a length of 2,000 μ.
m, measurement range 2,000 μm × 2,000 μm square, and number of measurement points n = 5. Table 1 shows the average value (nm) of the height difference between the highest part and the lowest part of each measurement. This value is 500 nm
In the following cases, it can be said that the inkjet coatability is good.

Evaluation of Dry-Solid Property The above composition was sucked into a fixed needle type microsyringe (Hamilton microsyringe, model number 701, needle inner diameter 0.13 mm), and the microsyringe was held vertically with the needle facing downward. With 1 μl of the above composition extruded from the beginning, 25
The state of the composition after observing for 24 hours in a room at 0 ° C. was observed. The results are shown in Table 1. In Table 1, when the composition was not dried and solidified at the needle tip, it was described as “good”, and when the composition was dried and solidified and the needle hole was clogged, it was described as “poor”.

Examples 2, 3, 4, 5 In Example 1, the types and addition amounts of the components [A], [B], [C], and [D], and the types of other solvents were changed. Composition solutions (2 to 5) were prepared and evaluated in the same manner as in Example 1 except that the results were as shown in Table 1. The results are shown in Table 1.
Shown in. In Table 1, the addition amount of each component is parts by weight, and "-" in the table means that the corresponding component is not added. In addition, [B] component, [C] component, [D] component
Abbreviations for components and other solvents are as follows.

Component [B-2]: Aronix M-400
(Manufactured by Toagosei Co., Ltd.) [C-2] component: 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals) [D-2] component: diethylene glycol monoethyl ether acetate S-1: diethylene glycol dimethyl ether S-2: Diethylene glycol ethyl methyl ether

Comparative Examples 1 and 2 In Examples 1 and 3, except that the component [D] was not added and instead S-1 or S-2 was used as the solvent,
A composition solution was prepared and evaluated in the same manner as in Example 1 or 3. The results are shown in Table 1.

[0066]

[Table 1]

[0067]

According to the present invention, a spacer which is suitable as a material for forming a spacer for a liquid crystal display device by an ink jet method and has excellent various properties such as adhesion, compressive strength and rubbing resistance can be easily prepared. There is provided a composition that can be formed into: Further, a spacer formed from the above composition, and a liquid crystal display device having the spacer and having excellent reliability are provided.

[0068]

[Brief description of drawings]

FIG. 1 is a schematic view showing a structure of a liquid crystal display element.

FIG. 2 is a schematic view showing a structure of a liquid crystal display element.

FIG. 3 is a schematic view showing a cross-sectional shape of a spacer.

Continued front page    F-term (reference) 2C056 EA24 FB01                 2H025 AB13 AC01 AD01 BC13 BC42                       CA00 CB13 CB14 CB16 CB41                       CC03 EA04 FA17                 2H089 LA09 LA16 MA07X NA07                       PA05 PA06 QA12 QA14 QA16                 4J011 PA65 PA66 PA68 PA69 PA70                       PB40 PC08 QA02 QA03 QA07                       QA09 UA01                 4J026 AA16 AA43 AA45 AA48 AA53                       AA55 AA56 AA57 AA68 AA69                       AC23 AC24 BA28 DA02 DB02                       DB09 DB36 FA05 FA09 GA07

Claims (3)

[Claims] 1. An [A] (a1) unsaturated carboxylic acid and / or
Or a copolymer of an unsaturated carboxylic acid anhydride, (a2) an epoxy group-containing unsaturated compound, and (a3) an olefinic unsaturated compound other than the above (a1) and (a2), [B] ethylenically unsaturated A radiation-sensitive resin used for forming a spacer by an inkjet method, which comprises a polymerizable compound having a bond, [C] a radiation-sensitive polymerization initiator, and [D] a solvent having a boiling point of 180 ° C. or higher at normal pressure. Composition. 2. A spacer formed from the radiation-sensitive resin composition according to claim 1. 3. A liquid crystal display device having the spacer according to claim 2.