JP2002278064A - Radiation sensitive resin composition, spacer for display panel and display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition capable of faithfully reproducing the design size of a mask pattern even by proximity exposure and capable of forming spacers for a display panel excellent in strength, heat resistance, etc., necessary for spacers and to provide spacers formed from the composition and a display panel having the spacers. SOLUTION: The composition contains [A] a copolymer of (a1) an ethylenically unsaturated carboxylic acid and/or an ethyenically unsaturated carboxylic acid anhydride, (a2) an epoxy-containing ethylenically unsaturated compound and (a3) another ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond and specified trihalomethyltriazines. A spacer is formed from the composition and a display panel is provided with the spacer.

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, a spacer for a display panel, and a display panel, and more particularly, to a material for forming a spacer used for a display panel such as a liquid crystal panel or a touch panel. The present invention relates to a radiation-sensitive resin composition suitable for the present invention, a display panel spacer formed therefrom, and a display panel having the display panel spacer.

[0002]

2. Description of the Related Art Conventionally, spacer particles such as glass beads and plastic beads having a predetermined particle size have been used in a liquid crystal panel in order to keep a constant distance between two substrates. Particles are randomly scattered on a transparent substrate such as a glass substrate.If spacer particles are present in the pixel formation area, the phenomenon of reflection of the spacer particles occurs, or incident light is scattered, and the contrast of the liquid crystal panel is reduced. There was a problem of lowering. In order to solve these problems, a method of forming a spacer by photolithography has been adopted. In this method, a photosensitive resin composition is applied onto a substrate, exposed to ultraviolet light through a predetermined mask, and then developed to form dot-like or stripe-like spacers. Since the spacer can be formed only at a predetermined position, the above-described problem is basically solved. By the way, when a spacer is formed by photolithography on a substrate used for an actual spacer forming process, for example, a color filter or the like, a proximity exposure machine is often used. For this proximity exposure,
Exposure is performed with a certain gap provided between the mask and the substrate coated with the photosensitive resin composition. Ideally, the exposure is performed in the same pattern as the mask, but the gap is filled with air or nitrogen, and the light passing through the opening (transparent portion) of the mask is diffused in the gap. Therefore, the exposure is made wider than the design size of the mask pattern. Therefore, the size of the cured product becomes larger than the size of the mask opening, and there is a problem in controlling the size and shape of the cured product.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a spacer for a display panel which can faithfully reproduce the design size of a mask pattern even by proximity exposure and which is excellent in strength, heat resistance and the like required as a spacer. It is an object of the present invention to provide a radiation-sensitive resin composition capable of forming the same, a display panel spacer formed therefrom, and a highly reliable display panel having the display panel spacer.

[0004]

According to the present invention, the above object is achieved by providing [A] (a1) an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic anhydride with (a)
2) an epoxy group-containing ethylenically unsaturated compound and (a3)
A copolymer with another ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond, and [C]
The following equation (1)

[0005]

Embedded image

(Wherein X represents halogen, A is CX
₃ or the following formula

[0007]

Embedded image

Wherein B, D and E each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkoxy group, an aryloxy group, a thioalkyl group, a thioaryl group, a halogen, Cyano group, nitro group, di (alkyl having 1 to 10 carbon atoms) amino group, carboxyl group, hydroxyl group, ketoalkyl or ketoaryl group having 1 to 10 carbon atoms, alkoxycarbonyl group or alkylcarbonyloxy group having 2 to 20 carbon atoms And m represents an integer of 1 to 5), and a photopolymerization initiator containing a trihalomethyltriazine represented by the formula (1):

The second object of the present invention is achieved by a display panel spacer formed from the radiation-sensitive resin composition. Further, a third object of the present invention is to provide:
This is achieved by a display panel having a display panel spacer formed from the radiation-sensitive resin composition.

Hereinafter, each component of the radiation-sensitive resin composition of the present invention will be described in detail. Copolymer [A] The component [A] in the present invention comprises (a1) an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic anhydride, (a2) an epoxy group-containing ethylenically unsaturated compound, and (a3) ) A copolymer with another ethylenically unsaturated compound (hereinafter, referred to as “copolymer [A]”). Among the components constituting the copolymer [A], (a1) an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid anhydride (hereinafter collectively referred to as “unsaturated carboxylic acid monomer” Examples of (a1) ”) include: monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids Mono [(meth) acryloyloxyalkyl] of a divalent or higher polycarboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate Esters];
And ω-carboxypolycaprolactone mono (meth)
Examples of the polymer include mono (meth) acrylates having a carboxyl group and a hydroxyl group at both terminals such as acrylate. Among these unsaturated carboxylic acid monomers (a1), acrylic acid, methacrylic acid, and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, solubility of the obtained copolymer in an aqueous alkali solution and easy availability. Are preferred. In the present invention, the unsaturated carboxylic acid monomer (a1)
They can be used alone or in combination of two or more.

In the copolymer [A], the content of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is as follows:
Preferably 5 to 40% by weight, particularly preferably 10 to 30%
% By weight. In this case, if the content of the repeating unit derived from the unsaturated carboxylic acid-based monomer (a1) is less than 5% by weight, the solubility in an aqueous alkali solution tends to decrease, while if it exceeds 40% by weight, And the solubility in an aqueous alkali solution may be too high.

Further, (a2) an epoxy group-containing ethylenically unsaturated compound (hereinafter referred to as “epoxy group-containing monomer (a
2) ". )), For example, epoxy alkyl acrylates such as glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate;
Glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, etc .; epoxy alkyl esters of methacrylic acid; α-glycidyl acrylate, α-n-propyl acryl Glycidyl acid, α-n
Α-alkyl acrylate epoxy alkyl esters such as -butyl glycidyl acrylate and α-ethyl acrylate 6,7-epoxyheptyl; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like Glycidyl ethers. Among these epoxy group-containing monomers (a2), glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl are preferred in view of copolymerization reactivity and spacer strength. Glycidyl ether, p-vinylbenzyl glycidyl ether and the like are preferred. In the present invention, the epoxy group-containing monomer (a2) can be used alone or in combination of two or more.

In the copolymer [A], the content of the repeating unit derived from the epoxy group-containing monomer (a2) is preferably from 10 to 70% by weight, particularly preferably from 20 to 60% by weight. In this case, the epoxy group-containing monomer (a2)
When the content of the repeating unit derived from is less than 10% by weight, the strength of the obtained spacer tends to decrease,
On the other hand, if it exceeds 70% by weight, the storage stability of the obtained copolymer tends to decrease.

Further, (a3) other ethylenically unsaturated compounds
Compound (hereinafter, simply referred to as “other monomer (a3)”).
For example, for example, methyl acrylate, i-acrylate
Alkyl acrylates such as ropyl; methacryl
Methyl acrylate, ethyl methacrylate, n-butyl methacrylate
Sec-butyl methacrylate, t-butyl methacrylate
Alkyl methacrylates such as tyl; acrylic acid
Cyclohexyl, 2-methylcyclohexyl acrylate
, Tricycloacrylate [5.2.1.0]^2,6 ]
Decane-8-yl, 2- (tricyclo [5.
2.1.0 ^2,6 ] Decane-8-yloxy) ethyl
Acrylates such as isobornyl acrylate
Ters; cyclohexyl methacrylate, methacrylic acid 2
-Methylcyclohexyl, tricyclomethacrylate [
5.2.1.0^2,6] Decane-8-yl, methacryl
Acid 2- (tricyclo [5.2.1.0]^2,6] Decane
8-yloxy) ethyl, isobornyl methacrylate, etc.
Alicyclic methacrylates; phenyl acrylate
Aryles such as benzyl and benzyl acrylate
Ter or aralkyl esters;
Of methacrylic acid such as benzyl, benzyl methacrylate, etc.
Esters or aralkyl esters; maleic acid
Diethyl, diethyl fumarate, diethyl itaconate, etc.
Dicarboxylic acid dialkyl esters; methacrylic acid 2-
Hydroxyethyl, 2-hydroxypropyl methacrylate
Hydroxyalkyl methacrylates such as
Tylene, α-methylstyrene, m-methylstyrene, p
-Vinyl flavors such as methylstyrene and p-methoxystyrene
Aromatic compounds; 1,3-butadiene, isoprene, 2,3
-Conjugated diene compounds such as dimethyl-1,3-butadiene
Acrylonitrile, methacrylonitrile,
Acrylamide, methacrylamide, vinyl chloride, vinyl chloride
Nilidene, vinyl acetate and the like can be mentioned. these
Among other monomers (a3), copolymerization reactivity and yield
The solubility of copolymers in aqueous alkali solutions?
2-methylcyclohexyl acrylate, methacryl
T-butyl acid, tricyclomethacrylate [5.2.1.
0^2,6] Decan-8-yl, styrene, p-methoxy
Styrene, 1,3-butadiene and the like are preferred. In the present invention
The other monomer (a3) may be used alone or in combination of two or more.
Can be used in combination.

In the copolymer [A], other monomers (a
The content of the repeating unit derived from 3) is preferably 10
It is preferably from 70 to 70% by weight, particularly preferably from 20 to 50% by weight. In this case, if the content of the repeating unit derived from the other monomer (a3) is less than 10% by weight, the storage stability of the obtained copolymer tends to decrease, while 70% by weight
If it exceeds, the solubility of the obtained copolymer in an aqueous alkali solution tends to decrease.

The copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, and has an appropriate solubility in an aqueous alkali solution and a special property. Can be easily cured by heating without the use of a suitable curing agent, and the radiation-sensitive resin composition of the present invention containing the copolymer causes undeveloped portions and reduced film thickness during development. Thus, a spacer having a predetermined pattern can be easily formed.

The copolymer [A] includes, for example, an unsaturated carboxylic acid monomer (a1) and an epoxy group-containing monomer (a2).
And another monomer (a3) by polymerization in a suitable solvent in the presence of a radical polymerization initiator. As the solvent used for the polymerization, for example, methanol, ethanol, n-propanol, i-
Alcohols such as propanol; tetrahydrofuran,
Ethers such as dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether,
Ethylene glycol monoalkyl ethers such as ethylene glycol mono-n-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n
Ethylene glycol monoalkyl ether acetates such as -propyl ether acetate and ethylene glycol mono-n-butyl ether acetate; ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propion , Ethylene glycol monoalkyl ether propionates such as ethylene glycol mono-n-butyl ether propionate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;
Diethylene glycol alkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; propylene glycol monomethyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n- Propylene glycol monoalkyl ether acetates such as propyl ether acetate and propylene glycol mono-n-butyl ether acetate;
Propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, propylene glycol mono-n-
Propylene glycol monoalkyl ether propionates such as butyl ether propionate; toluene,
Aromatic hydrocarbons such as xylene; methyl ethyl ketone;
2-pentanone, 3-pentanone, cyclohexanone,
Ketones such as 4-hydroxy-4-methyl-2-pentanone;

Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate,
Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, 2-n-propoxypropionic acid n-
Propyl, n-butyl 2-n-propoxypropionate, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-n-butoxypropionate −
Butyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n- 3-methoxypropionate
Propyl, n-butyl 3-methoxypropionate, 3-
Methyl ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, 3
-N-butyl ethoxypropionate, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, 3-
Methyl n-butoxypropionate, ethyl 3-n-butoxypropionate, n- 3-n-butoxypropionate
Propyl, alkyl alkoxypropionates such as n-butyl 3-n-butoxypropionate,

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, methyl lactate, ethyl lactate, n-lactate
Propyl, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-3-hydroxypropionate Propyl, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxy N-propyl acetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyl n-propoxyacetate, n-butyl n-propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate , N-butoxyacetic acid n Propyl, and the like can be given other esters such as n- butoxy acetate n- butyl.

Among these solvents, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, alkyl alkoxypropionates and the like are preferred. The solvents may be used alone or in combination of two or more.

The radical polymerization initiator used for the polymerization is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2 ′
-Azobis- (2,4-dimethylvaleronitrile),
Azo compounds such as 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butylperoxy)
Organic peroxides such as cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used in combination with a reducing agent to form a redox initiator. These radical polymerization initiators can be used alone or in combination of two or more. The copolymer [A] thus obtained
May be used as a solution for preparing the radiation-sensitive resin composition, or may be separated from the solution and used for preparing the radiation-sensitive resin composition.

The weight average molecular weight (hereinafter, referred to as “Mw”) of the copolymer [A] in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 2,2.
000-100,000, preferably 5,000-5
000. In this case, if Mw is less than 2,000, the developability of the resulting film, the residual film ratio, etc. may be reduced, or the pattern shape, heat resistance, etc. may be impaired. However, there is a possibility that the resolution is reduced or the pattern shape is impaired.

Polymerizable Compound [B] The component [B] used in the present invention is a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as “polymerizable compound [B]”). Although it is not particularly limited, monofunctional, difunctional or trifunctional or more (meth) acrylic acid esters are preferable from the viewpoint of good polymerizability and improving the strength of the obtained spacer, Particularly, trifunctional or higher functional (meth) acrylates are preferable.

The monofunctional (meth) acrylates include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl Methacrylate,
3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-acryloyloxyethyl-2-
Examples thereof include hydroxypropyl phthalate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, and commercial products such as Aronix M-101, M-111, and M-114 (manufactured by Toagosei Co., Ltd.) ); KAYARAD TC-110S, T
C-120S (manufactured by Nippon Kayaku Co., Ltd.);
8, 2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

The bifunctional (meth) acrylates include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate,
1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, and the like. Can be used as a commercial product,
For example, Aronix M-210, M-240, M
-6200 (manufactured by Toa Gosei Co., Ltd.), KAYARAD H
DDA, HX-220, R-604 (manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 260, 312, 335H
P (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

Further, the trifunctional or higher functional (meth) acrylates include, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol Erythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate,
Tri (2-methacryloyloxyethyl) phosphate and the like can be mentioned, and as commercial products, for example,
Aronix M-309, M-400, M-40
5, the same M-450, the same M-7100, the same M-8030,
M-8060 and TO-1450 (Toagosei Co., Ltd.)
KAYARAD TMPTA, DPHA, D
PCA-20, DPCA-30, DPCA-60,
DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 295, 300, 360, GPT, 3PA, and 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.). These monofunctional, difunctional or trifunctional or higher (meth) acrylic esters can be used alone or in combination of two or more.

Photopolymerization initiator [C] The photopolymerization initiator referred to in the present invention means that the polymerization of the polymerizable compound [B] is started by exposure to visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray or the like. And generates an active species which can be obtained by the following formula (1)

[0028]

Embedded image

(Wherein X represents halogen, A is CX
₃ or the following formula

[0030]

Embedded image

And B, D and E each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkoxy group, an aryloxy group, a thioalkyl group, a thioaryl group, a halogen, Cyano group, nitro group, di (alkyl having 1 to 10 carbon atoms) amino group, carboxyl group, hydroxyl group, ketoalkyl or ketoaryl group having 1 to 10 carbon atoms, alkoxycarbonyl group or alkylcarbonyloxy group having 2 to 20 carbon atoms And m represents an integer of 1 to 5).

The trihalomethyltriazines represented by the formula (1) include, for example, 2,4,6-tris (trichloromethyl) -s-triazine, 2-phenyl-4,6-
Bis (trichloromethyl) -s-triazine, 2- (4
-Chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-chlorophenyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (2-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3- Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (4-methylthiophenyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (3-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methylthiophenyl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (4-methoxynaphthyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(3-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy -Β-styryl) -4,6-
Bis (trichloromethyl) -s-triazine, 2- (3
-Methoxy-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxy-β
-Styryl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (3,4,5-trimethoxy-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (3-methylthio-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methylthio-β-styryl) -4,6-bis (trichloromethyl) -s- Triazine, the following formula (2)

[0033]

Embedded image

(In the formula (2), X represents a halogen atom.
Examples of such a halogen atom include fluorine, chlorine, and bromine. R ¹ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyl group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, Number 1
An alkylthio group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and 6 to 1 carbon atoms
0 arylthio group, di (alkyl having 1 to 10 carbon atoms)
An amino group, a di (aryl having 6 to 10 carbon atoms) amino group,
An alkylcarbonyl group having 2 to 11 carbon atoms, 7 to 1 carbon atoms
1 represents an arylcarbonyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkylcarbonyloxy group having 2 to 10 carbon atoms. R ² and R ³ each independently represent an alkyl group having 1 to 10 carbon atoms or 6 to 10 carbon atoms;
Is an aryl group. I is an integer of 1 to 4.
Examples of the halogen atom for R ¹ , R ⁴ and R ⁵ include fluorine, chlorine and bromine. And the like.

Here, examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and decyl. These may be linear or branched. Examples of the C1-C10 alkoxyl group and the C1-C10 alkylthio group include C1-C10
Specific examples thereof include a corresponding group having an alkyl group exemplified as the above alkyl group, such as a methoxy group and a methylthio group.

Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, and naphthyl. An aryloxy group having 6 to 10 carbon atoms and 6 carbon atoms
Specific examples of the arylthio group having 10 to 10 include, for the aryl group having 6 to 10 carbon atoms, a corresponding group having the above-described aryl group, such as a phenoxy group and a phenylthio group.

Specific examples of the di (C 1-10 alkyl) amino group include a corresponding group having the alkyl group exemplified for the C 1-10 alkyl group, for example, a di (methyl) amino group. be able to. In this case, the two alkyl groups may be the same or different.
Specific examples of the di (C6 to C10 aryl) amino group include a corresponding group having an aryl group exemplified for the C6 to C10 aryl group, such as a di (phenyl) amino group. . In this case, the two aryl groups may be the same or different.

As the alkylcarbonyl group having 2 to 11 carbon atoms, a corresponding group having the alkyl group exemplified for the alkyl group having 1 to 10 carbon atoms, for example, methylcarbonyl group (acetyl group), ethylcarbonyl group (propionyl group) And the like can be given as specific examples. Carbon number 7 ~
The arylcarbonyl group of 11 has 6 to 10 carbon atoms.
And a corresponding group having an aryl group exemplified for the aryl group, for example, a phenylcarbonyl group. As the alkoxycarbonyl group having 2 to 10 carbon atoms and the alkylcarbonyloxy group having 2 to 10 carbon atoms, corresponding groups having the alkyl groups exemplified for the alkyl group having 1 to 10 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group And a methylcarbonyloxy group, an ethylcarbonyloxy group, and the like.

Of these trihalomethyltriazines, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s
-Triazine and the compound represented by the above formula (2) are preferably used. Preferred trihalomethyltriazines represented by the above formula (2) include, for example, 2-
(4-Diethylamino-2-methyl-β-styryl)-
4,6-bis (trichloromethyl) -s-triazine, 2
-(4-diphenylamino-2-methyl-β-styryl)
-4,6-bis (trichloromethyl) -s-triazine,
2- (2-phenylamino-4-methoxy-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-isobutylamino-2-methyl-β-styryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-dimethylamino-2-cyano-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-diethylamino- 4-methylthio-β
-Styryl) -4,6-bis (trichloromethyl) -s-triazine and the like.

Of these compounds, 2- (4-diethylamino-2-methyl-β-styryl) -4,6-bis
(Trichloromethyl) -s-triazine, 2- (4-isobutylamino-2-methyl-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-diphenylamino-2- Methyl-β-styryl) -4,6-
Bis (trichloromethyl) -s-triazine and the like can be particularly preferably used.

The amount of the photopolymerization initiator [C] used in the present invention is preferably 1 to 15 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the copolymer [A]. is there. Use within this range provides a radiation-sensitive resin composition having an excellent balance between the heat resistance and solvent resistance of the spacer and the controllability of the pattern shape after development.

The photopolymerization initiator [C] can be used in combination with another photopolymerization initiator, if desired.
Examples of such other photopolymerization initiators include α-diketones such as benzyl and diacetyl; benzoin, o-
Acyloins such as toluoin, p-toluoin and anisoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin i-propyl ether; acetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2 , 2'-Dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-
Acetophenones such as [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; anthraquinone, 1,4 Quinones such as naphthoquinone; halogen compounds such as phenacyl chloride, tribromomethylphenylsulfone, and tris (trichloromethyl) -s-triazine; 2,4,6
Acylphosphine oxides such as -trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide; and peroxides such as benzoyl peroxide and di-t-butyl peroxide.

Other commercially available photopolymerization initiators include, for example, IRGACURE-184, 369, 500, 651, 907, 819, 1700,
Darocur-1173, 1116, 2959,
1664, 4043 (manufactured by Ciba Specialty Chemicals), KAYACURE-DETX, MB
P, DMBI, EPA, OA (Nippon Kayaku Co., Ltd.)
VICURE-10, 55 (STAUFFER)
Co. LTD), TRIGONALP1 (AKZ
O Co. LTD), SANDORAY 1000
(Sandoz Co. Ltd.), DEAP (AP
JOHN Co. LTD), QUANTACURE
-PDO, ITX, EPD (WARD BLEKI
NSOP Co. LTD).

In the present invention, by using these other photopolymerization initiators together with the photopolymerization initiator [C], the compressive strength of the spacer, the adhesion to the substrate, and the like can be further improved, and the cross-section of the pattern can be improved. It is also possible to control the shape.

The other photopolymerization initiator may be used alone or
A mixture of more than one species can be used. The proportion of the other photopolymerization initiator to be used is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, particularly preferably 30 parts by weight or less based on 100 parts by weight of the photopolymerization initiator [C]. In this case, the usage ratio of the other photopolymerization initiator is 100
If the amount exceeds the weight part, the size of the obtained pattern may be larger than the design size of the mask pattern beyond an allowable range.

Further, the photopolymerization initiator [C] can be used in combination with a sensitizer in the presence or absence of another photopolymerization initiator to further improve the sensitivity. Examples of the sensitizer include N-methyldiethanolamine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, and p-dimethylaminobenzoate. Examples thereof include i-amyl acid, 2,4-diethylthioxanthone, and thioxanthone-4-sulfonic acid. Among these sensitizers, 4,4'-bis (diethylamino) benzophenone, 2,4-diethylthioxanthone and the like are preferable.

The sensitizers can be used alone or in combination of two or more. The use ratio of the sensitizer is preferably 40 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the photopolymerization initiator [C]. In this case, if the use ratio of the sensitizer exceeds 40 parts by weight, development residual tends to occur easily.

Other Additives The radiation-sensitive resin composition of the present invention may contain additives other than the above components, if necessary, as long as the desired effects of the present invention are not impaired. As the additive,
Examples of the surfactant include a surfactant for improving coatability. Commercially available surfactants include, for example, BM-
1000, BM-1100 (manufactured by BM CHEMIE), Megafac F142D, F172, F17
3, F183 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-135, FC-170C, FC-4
30, FC-431 (manufactured by Sumitomo 3M Limited), Surflon S-112, S-113, S-131, S-141, S-145, S-382, and SC-1
01, SC-102, SC-103, SC-10
4. SC-105, SC-106 (Asahi Glass Co., Ltd.)
EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), SH-28PA, SH-190,
SH-193, SZ-6032, SF-8428, DC
-57 and DC-190 (manufactured by Toray Silicone Co., Ltd.).

Examples of the surfactants other than the commercially available products include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene n-octyl. Polyoxyethylene aryl ethers such as phenyl ether and polyoxyethylene n-nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and commercially available products As KP3
Polyflow No. 41 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5
7, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These surfactants can be used alone or in combination of two or more. The amount of surfactant is
The copolymer [A] is preferably 5 to 100 parts by weight.
It is at most 2 parts by weight, more preferably at most 2 parts by weight. In this case, if the amount of the surfactant exceeds 5 parts by weight, the film tends to be roughened during coating.

In order to improve the adhesion to the substrate, an adhesion aid may be used. As the adhesion aid, a functional silane coupling agent is preferable, and examples thereof include a silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. More specifically, trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3 ', 4'-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. These adhesion aids can be used alone or in combination of two or more. The amount of the adhesion aid is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In this case, if the compounding amount of the adhesion aid exceeds 20 parts by weight, development residue tends to easily occur.

Radiation-Sensitive Resin Composition The radiation-sensitive resin composition of the present invention comprises a copolymer [A],
It is prepared by uniformly mixing components including the polymerizable compound [B] and the photopolymerization initiator [C]. When preparing the radiation-sensitive resin composition, an appropriate solvent is usually added to obtain a composition solution. As the solvent used for preparing the radiation-sensitive resin composition solution, one that uniformly dissolves each component constituting the radiation-sensitive resin composition and that does not react with each component is used. The same solvents as those exemplified for the polymerization for producing the copolymer [A] can be used. Among these solvents, ethylene glycol monoalkyl ethers, ethylene glycol monoalkyl ether acetates, diethylene glycol alkyl ethers and propylene are preferred in view of the solubility of each component, the reactivity with each component, and the ease of forming a coating film. Preferred are glycol monoalkyl ether acetates, alkyl alkoxypropionates, and the like.
The solvents may be used alone or in combination of two or more.

In preparing the radiation-sensitive resin composition solution, a high-boiling solvent may be used in combination with the solvent. Examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N
-Methylformanilide, N-methylacetamide,
N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether,
Di-n-hexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol,
1-nonanol, benzyl alcohol, benzyl acetate,
Examples thereof include ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate. These high-boiling solvents can be used alone or in combination of two or more.
The composition solution prepared as described above, if necessary,
It can also be used after being filtered by a millipore filter having a pore diameter of, for example, about 0.2 to 0.5 μm.

Formation of Spacer for Display Panel The radiation-sensitive resin composition of the present invention is particularly suitable as a material for forming a spacer for a display panel such as a liquid crystal panel or a touch panel. When forming a spacer for a display panel, a coating solution is applied to the surface of a substrate and then prebaked to remove a solvent to form a coating film. As a method of applying the composition solution, for example,
Appropriate methods such as a spray method, a roll coating method, and a spin coating method can be adopted. The conditions of the pre-bake vary depending on the type of each component, the blending ratio, and the like, but are usually about 70 to 90 ° C. for about 1 to 15 minutes. Next, the prebaked coating film is exposed and polymerized through a mask having a predetermined pattern, and then developed with a developer.
An unnecessary portion is removed to form a pattern. As radiation used for exposure, visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray and the like can be appropriately selected, but ultraviolet light is preferable. The developing method may be, for example, any of a liquid puddle method, an immersion method, and a shower method, and the development time is usually 30 to 180 seconds.

Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; 3 such as trimethylamine, methyldiethylamine, ethyldimethylamine and triethylamine;
Tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7 -Alicyclic tertiary amines such as -undecene, 1,5-diazabicyclo [4.3.0] -5-nonene; aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; tetramethylammonium hydroxide And an aqueous solution of an alkaline compound such as a quaternary ammonium salt such as tetraethylammonium hydroxide. In addition, a suitable amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant may be added to the aqueous solution of the alkaline compound.
After the development, unnecessary portions are removed, for example, by washing with running water for 30 to 90 seconds, for example, and then a predetermined pattern is formed by blowing compressed air or compressed nitrogen and air-drying. Thereafter, the pattern is formed by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, for 5 to 30 minutes on the hot plate, and for 30 to 9 in the oven.
By performing the heat treatment for 0 minutes, the target spacer can be obtained.

Display Panel The display panel of the present invention has a spacer formed as described above from the radiation-sensitive resin composition of the present invention. Examples of such a display panel include a liquid crystal display panel and a touch panel.

[0056]

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
It is not limited to these examples.

[0057]

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 200 parts by weight of diethylene glycol methyl ethyl ether, followed by methacrylic acid. acid 20 parts by weight, 45 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene were charged methacrylic acid tricyclo [5.2.1.0 ^{2, 6]} decan-8-yl 25 parts by weight. Thereafter, after the atmosphere was replaced with nitrogen, the temperature of the solution was increased to 70 ° C. while stirring gently, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution of the copolymer [A-1]. The solids concentration of this solution is 3
Mw of the copolymer [A-1] is 2% by weight.
It was 4,000.

Synthesis Example 2 A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by methacrylic acid. 20 parts by weight, 50 parts by weight of glycidyl methacrylate, and 25 parts by weight of styrene were charged. Then, after purging with nitrogen, 5 parts by weight of 1,3-butadiene was further charged, and the temperature of the solution was increased to 70 ° C. with gentle stirring, and the temperature was maintained for 5 hours to polymerize the copolymer [A -2]. The solid content of this solution was 33.3% by weight, and the copolymer [A
-2] was 20,000.

Example 1 Preparation of Radiation-Sensitive Resin Composition 100 parts by weight (solid content) of a solution of the copolymer [A-1] obtained in Synthesis Example 1, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate 80 parts by weight of a mixture of
After dissolving 8 parts by weight of-(4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine in propylene glycol monomethyl ether acetate so that the solid content concentration becomes 35% by weight, .2
The solution was filtered through a micrometer millipore filter, and the composition solution (S-
1) was prepared.

The composition solution (S-1) for forming a spacer was applied on a glass substrate using a spinner, and then prebaked on a hot plate at 80 ° C. for 3 minutes to form a coating film. Next, a mask having a predetermined pattern (10 μm) was applied to the obtained coating film in air.
m × 10 μm) with an exposure gap of 100 μm and an exposure intensity at a wavelength of 365 nm of 100 W / m ^2.
UV light proximity exposure was performed for 30 seconds.
Thereafter, development was performed with a 0.2% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute to remove unnecessary portions, followed by washing with pure water for 1 minute to obtain a pattern. The resulting pattern is then placed in an oven,
Heating was performed at 220 ° C. for 60 minutes to obtain a spacer having a predetermined pattern and a height of 5 μm.

[0061] For the evaluation obtained spacer, it was evaluated the following items. Table 1 shows the evaluation results. (1) Dimension (width) of cross section at bottom of pattern Measured with a scanning electron microscope. (2) Spacer strength A microcompression tester (MCTM-200, manufactured by Shimadzu Corporation) was used to evaluate as follows. Breaking load (measuring temperature: 25 ° C);
A compressive load in the vertical direction was applied at a constant speed (2.65 mN / sec) by a plane indenter having a diameter of 50 μm, and the load when a crack or break occurred in the spacer was measured and defined as a break load. Breaking strain (measuring temperature: 25 ° C.): The value obtained by dividing the compressive displacement when the breaking load was reached by the height of the spacer (5 μm) was defined as breaking strain. (3) Heat resistance The dimensional change rate of the pattern height when the spacer was heated at 240 ° C. for 60 minutes in an oven was determined.

Example 2 The procedure of Example 1 was repeated, except that the solution of the copolymer [A-2] obtained in Synthesis Example 2 was used instead of the solution of the copolymer [A-1]. A composition solution (S-2) was prepared, a spacer was formed, and evaluated. Table 1 shows the evaluation results.

Example 3 As a photopolymerization initiator [C], 5 parts by weight of 2- (4-diethylamino-2-methyl-β-styryl) -4,6-bis (trichloromethyl) -s-triazine and bis (2 ,
4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE-819) except that 10 parts by weight of the composition solution (S-
3) was prepared, a spacer was formed, and evaluated. Table 1 shows the evaluation results.

Example 4 Instead of 8 parts by weight of 2- (4-diethylamino-2-methyl-β-styryl) -4,6-bis (trichloromethyl) -s-triazine as the photopolymerization initiator [C], 2
-(4-isobutylamino-2-methyl-β-styryl)
-4,6-bis (trichloromethyl) -s-triazine 1
A composition solution (S-4) was prepared, and a spacer was formed and evaluated in the same manner as in Example 1 except that 0 part by weight was used. Table 1 shows the evaluation results.

[0065]

[Table 1]

[0066]

According to the present invention, the radiation sensitivity which can faithfully reproduce the design size of a mask pattern even by proximity exposure and can form a spacer for a display panel which is excellent in strength and heat resistance required as a spacer. A resin composition, a spacer for a display panel obtained therefrom, and a display panel having the spacer are provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) G03F 7/032 501 G03F 7/032 501 (72) Inventor Kazuaki Niwa 2-11 Tsukiji, Chuo-ku, Tokyo No. 24 F-term in JSR Co., Ltd. (reference) 2H025 AA10 AA13 AB20 AC01 AD01 BC14 BC32 BC42 BD23 CA14 CA28 CB43 FA03 FA17 FA29 4J011 PA69 PA70 PA86 PB40 PC02 PC08 QA03 QA13 QA23 QA24 QA34 QA45 QA46 RA01 RA10 SA01 AA48 AA54 AA59 AB04 AC23 AC24 BA27 BA28 BA29 BA30 DA02 DA12 DB24 DB36 FA05 GA07 GA08

Claims (5)

[Claims] 1. [A] (a1) an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic anhydride, (a2) an epoxy group-containing ethylenically unsaturated compound and (a3) another ethylenically unsaturated A copolymer with a compound,
[B] a polymerizable compound having an ethylenically unsaturated bond, and [C] a compound represented by the following formula (1): (Wherein X represents halogen, A is CX ₃ or the following formula: And B, D and E each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkoxy group, an aryloxy group, a thioalkyl group, a thioaryl group, a halogen, a cyano group, A nitro group, a di (alkyl having 1 to 10 carbon atoms) amino group, a carboxyl group, a hydroxyl group, a ketoalkyl group or a ketoaryl group having 1 to 10 carbon atoms, an alkoxycarbonyl group or an alkylcarbonyloxy group having 2 to 20 carbon atoms, And m represents an integer of 1 to 5). A radiation-sensitive resin composition comprising a photopolymerization initiator containing a trihalomethyltriazine represented by the following formula: 2. A compound represented by the formula (1):
Is represented by the following formula (2):(Wherein X represents a halogen atom;¹, R^FourAnd R
^FiveIs independently a hydrogen atom, a halogen atom,
Group, nitro group, carboxyl group, hydroxyl group, carbon number 1-1
0 alkyl group, alkoxyl group having 1 to 10 carbon atoms, carbon
An alkylthio group having a prime number of 1 to 10 and an ant having a carbon number of 6 to 10
Aryl group having 6 to 10 carbon atoms, 6 carbon atoms
Arylthio group, di (alkoxy having 1 to 10 carbon atoms)
Ru) amino group, di (aryl having 6 to 10 carbon atoms) amino
Group, alkylcarbonyl group having 2 to 11 carbon atoms, 7 carbon atoms
An arylcarbonyl group having from 11 to 11 carbon atoms having 2 to 10 carbon atoms;
A oxycarbonyl group or an alkyl group having 2 to 10 carbon atoms
A carbonyloxy group; ^TwoAnd R^ThreeAre independent
An alkyl group having 1 to 10 carbon atoms or 6 to 10 carbon atoms
An aryl group and i represents an integer of 1 to 4; )so
The trihalomethyltriazines represented
The radiation-sensitive resin composition according to claim 1, which is a feature. 3. The radiation-sensitive resin composition according to claim 1, wherein the radiation-sensitive resin composition is for forming a spacer for a display panel. 4. A spacer for a display panel formed from the radiation-sensitive resin composition according to claim 3. 5. A display panel having a display panel spacer formed from the radiation-sensitive resin composition according to claim 3.