KR100839300B1 - Radiation Sensitive Resin Composition, Spacer for Display Panel, and Display Panel - Google Patents

Abstract

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

Radiation-sensitive resin composition, display panel, spacer

Description

Radiation-sensitive resin composition, spacer for display panel, and display panel {Radiation Sensitive Resin Composition, Spacer for Display Panel, and Display Panel}

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

In the liquid crystal panel, spacer particles such as glass beads and plastic beads having a predetermined particle diameter have conventionally been used in order to keep the two substrate gaps constant, but these spacer particles are randomly scattered on transparent substrates such as glass substrates. Therefore, when the spacer particles exist in the pixel formation region, the spacer particles may be reflected, or incident light may be scattered and the contrast of the liquid crystal panel may be lowered.

Thus, a method of photolithographically forming spacers has been used to solve these problems. In this method, the photosensitive resin composition is applied onto a substrate and exposed to ultraviolet rays through a predetermined mask and then developed to form a dot or stripe spacer, and the spacer is formed only at a predetermined place other than the pixel formation region. This can basically solve the above problems.

By the way, when forming a spacer by photolithography on the board | substrate used for an actual spacer formation process, for example, a color filter, etc., a proximity exposure machine is often used. In this proximity exposure, a constant gap is provided between a mask and the board | substrate which apply | coated the photosensitive resin composition, and it exposes. The exposure is ideally exposed in a pattern according to a mask, but since the gap is filled with air or nitrogen, and light passing through the opening (transparent portion) of the mask diffuses and widens in this gap portion, it is larger than the design size of the mask pattern. Wide exposure. Therefore, the dimension of hardened | cured material became larger than the dimension of a mask opening part, and there existed a problem in the dimension and shape control of hardened | cured material.

The subject of this invention is a radiation sensitive resin composition which can faithfully reproduce the design size of a mask pattern by proximity exposure, and can form the spacer for display panels excellent in the strength, heat resistance, etc. which are required as a spacer, and The present invention provides a highly reliable display panel having a method for forming a display panel spacer, a display panel spacer formed therefrom, and a display panel spacer.

According to the present invention,

[A] a copolymer of (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride with (a2) an epoxy group-containing ethylenically unsaturated compound and (a3) another ethylenically unsaturated compound,

[B] a polymerizable compound having an ethylenically unsaturated bond, and

(C) It is achieved by the radiation sensitive resin composition characterized by containing the photoinitiator containing trihalomethyl triazine represented by following General formula (1).

In the formula, X represents a halogen,

A represents a group represented by CX ₃ or the following formula,

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

Moreover, the 2nd subject of this invention is at least

① process of forming the coating film of said radiation sensitive resin composition on a board | substrate,

② a step of irradiating at least a portion of the coating film with radiation,

③ developing process,

④ heat treatment process

It is achieved by a method for forming a spacer for a display panel comprising a.

Moreover, the 3rd subject of this invention is achieved by the spacer for display panels formed from the said radiation sensitive resin composition.

The 4th subject of this invention is achieved by the display panel which has a display panel spacer formed from the said radiation sensitive resin composition.

Hereinafter, each component of the radiation sensitive resin composition of this invention is demonstrated in detail.

Copolymer [A]

In the present invention, the component [A] is composed of (a1) an ethylenically unsaturated carboxylic acid and / or an ethylene unsaturated carboxylic anhydride, (a2) an epoxy group-containing ethylenically unsaturated compound, and (a3) another ethylenically unsaturated compound. Copolymers (hereinafter referred to as "copolymer [A]").

Among the components constituting the copolymer [A], (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride (hereinafter, collectively referred to as "unsaturated carboxylic acid monomer (a1)") ), For example, monocarboxylic acids, such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Mono [(meth) of divalent or more polyvalent carboxylic acids, such as these dicarboxylic anhydrides, succinic acid mono [2- (meth) acryloyloxyethyl], and phthalic acid mono [2- (meth) acryloyloxyethyl] ) Acryloyloxyalkyl] esters; And mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -Carboxypolycaprolactone mono (meth) acrylate.

Among these unsaturated carboxylic acid monomers (a1), acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity, solubility in an aqueous alkali solution, and availability of the copolymer obtained.

In the present invention, the unsaturated carboxylic acid monomer (a1) can be used alone or in combination of two or more thereof.

In the copolymer [A], the content of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight. In this case, when the content rate of the repeating unit derived from an unsaturated carboxylic acid monomer (a1) is less than 5 weight%, there exists a tendency for the solubility to aqueous alkali solution to fall, and when it exceeds 40 weight%, it is solubility to aqueous alkali solution. This may grow too large.

Moreover, as (a2) epoxy group containing ethylenically unsaturated compound (henceforth "epoxy group containing monomer (a2)"), for example, glycidyl acrylate, 2-methyl glycidyl acrylate, 3, 4- epoxy butyl acrylate. Acrylic acid epoxy alkyl esters such as acrylic acid 6,7-epoxyheptyl; Methacrylic acid epoxy alkyl esters such as methacrylic acid glycidyl, methacrylic acid 2-methylglycidyl, methacrylic acid 3,4-epoxybutyl, methacrylic acid 6,7-epoxyheptyl; α-ethylacrylic acid Α-alkylacrylic acid epoxy alkyl esters such as glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl and α-ethyl acrylate 6,7-epoxyheptyl; and glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether.

Among these epoxy group-containing monomers (a2), methacrylate glycidyl, methacrylic acid 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether and m-vinylbenzyl glycid in terms of copolymerization reactivity and the strength of the spacer Dyl ether, p-vinylbenzyl glycidyl ether, etc. are preferable.

In this invention, an epoxy group containing monomer (a2) can be used individually or in combination of 2 or more types.

In the copolymer [A], the content rate of the repeating unit derived from an epoxy group containing monomer (a2) becomes like this. Preferably it is 10 to 70 weight%, Especially preferably, it is 20 to 60 weight%. In this case, when the content rate of the repeating unit derived from an epoxy group containing monomer (a2) is less than 10 weight%, there exists a tendency for the intensity | strength of the spacer obtained to fall, and when it exceeds 70 weight%, the storage stability of the copolymer obtained will fall. There is this.

Moreover, as another ethylenically unsaturated compound (henceforth "other monomer (a3)") of (a3), For example, alkyl acrylates, such as methyl acrylate and i-propyl acrylate; Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate; Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl acrylate Acrylic alicyclic esters such as isoboroyl acrylate; Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, 2-methacrylic acid (tricyclo [5.2.1.0 ^{2, 6} ] Methacrylic acid alicyclic esters such as decan-8-yloxy) ethyl and isobornyl methacrylate; Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; Aryl esters or aralkyl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate; Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid; Methacrylic acid hydroxyalkyl esters such as methacrylic acid 2-hydroxyethyl and methacrylic acid 2-hydroxypropyl; Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene; In addition to conjugated diene-based compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, Vinyl acetate etc. are mentioned.

Among these other monomers (a3), 2-methylcyclohexyl acrylate, t-butyl methacrylate and tricyclo methacrylate [5.2.1.0 ^2,6] in terms of copolymerization reactivity and solubility in an aqueous alkali solution of the resulting copolymer. ] Decane-8-yl, styrene, p-methoxystyrene, 1,3-butadiene and the like are preferred.

In this invention, another monomer (a3) can be used individually or in combination of 2 or more types.

In the copolymer [A], the content rate of the repeating unit derived from another monomer (a3) becomes like this. Preferably it is 10 to 70 weight%, Especially preferably, it is 20 to 50 weight%. In this case, when the content rate of the repeating unit derived from another monomer (a3) is less than 10 weight%, the storage stability of the copolymer obtained tends to fall, and when it exceeds 70 weight%, the solubility with respect to the aqueous alkali solution of the copolymer obtained is It tends to be lowered.

The copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, has moderate solubility in aqueous alkali solution, and can be easily cured by heating without using a special curing agent. In addition, the radiation sensitive resin composition of this invention containing this copolymer can form a spacer of a predetermined pattern easily, without developing waste and film | membrane reduction at the time of image development.

As a specific example of the copolymer [A] which can be preferably used by this invention, For example, methacrylic acid / glycidyl methacrylate / styrene copolymer,                     

Methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer,

Methacrylic acid / methacrylate glycidyl / styrene / 1,3-butadiene copolymer,

Methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer,

Methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / 1,3-butadiene copolymer,

Methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer,

Methacrylic acid / methacrylate glycidyl / benzyl methacrylate / styrene copolymer,

Methacrylic acid / methacrylate glycidyl / benzyl methacrylate / styrene / 1,3-butadiene copolymer,

Methacrylic acid / methacrylate glycidyl / benzyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer,

Methacrylic acid / methacrylate glycidyl / phenylmaleimide / styrene / 1,3-butadiene copolymer,

Methacrylic acid / methacrylate glycidyl / cyclohexylmaleimide / styrene / 1,3-butadiene copolymer,                     

Methacrylic acid / methacrylic acid glycidyl / 2-hydroxyethyl methacrylate / styrene / 1,3-butadiene copolymer,

Methacrylic acid / glycidyl acrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer,

Methacrylic acid / glycidyl acrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer,

Methacrylic acid / P-vinylbenzylglycidylether / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer,

Methacrylic acid / P-vinylbenzylglycidylether / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer,

Acrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer,

Acrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer,

Acrylic acid / glycidyl acrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer,

Acrylic acid / glycidyl acrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / styrene / 1, 3- butadiene copolymer is mentioned.

Among them, methacrylic acid / methacrylate glycidyl / styrene / 1,3-butadiene copolymer,

Methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer,

Methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer,

Methacrylic acid / glycidyl acrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer,

Acrylic acid / glycidyl acrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer can be preferably used.

Copolymer [A] can be produced, for example, by polymerizing an unsaturated carboxylic acid monomer (a1), an epoxy group-containing monomer (a2) and another monomer (a3) in a suitable solvent in the presence of a radical polymerization initiator.

As a solvent which can be used for the said superposition | polymerization, for example,

Alcohols such as methanol, ethanol, n-propanol and i-propanol;

Ethers such as tetrahydrofuran and dioxane;

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether and ethylene glycol mono-n-butyl ether;

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate;

Ethylene glycol monoalkyl ether propionate, such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, and ethylene glycol mono-n-butyl ether propionate Nates;

Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate;

Propylene glycol monoalkyl ether propionate, such as propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, and propylene glycol mono-n-butyl ether propionate Nates;

Aromatic hydrocarbons such as toluene and xylene;

Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone;

Methyl 2-methoxypropionate, 2-methoxy ethylpropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxy N-propyl propionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionic acid, 2-n-propoxypropionic acid n-butyl, 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, 3 N-butyl ethoxypropionate, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propoxypropionate Lofil, 3-n-propoxypropionate n-butyl, 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, 3-n-butoxypropionate n-propyl, 3-n-butoxypropionate n Alkyl alkoxypropionates such as butyl or

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid n-propyl, hydroxyacetic acid n-butyl, methyl lactate, ethyl lactate, n-propyl lactate N-butyl lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl hydroxypropionate N-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid n-propyl, methoxyacetic acid n-butyl, methyl ethoxyacetic acid , Ethoxy acetate, ethoxy acetate n-propyl, ethoxy acetate n-butyl, n-propoxy acetate, n-propoxy acetate, n-propoxy acetate n-propyl, n-propoxy acetate n- Butyl, n-butoxyacetic acid And other esters such as ethyl, n-butoxyacetate, n-butoxyacetate n-propyl, and n-butoxyacetate n-butyl.

Among these solvents, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, alkyl alkoxypropionates and the like are preferable.

The said solvent can be used individually or in mixture of 2 or more types.

Moreover, as a radical polymerization initiator used for the said superposition | polymerization, although it does not specifically limit, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile ), Azo compounds such as 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate and 1,1-bis (t-butylperoxy) cyclohexane; Hydrogen peroxide and the like. In addition, when using a peroxide as a radical polymerization initiator, it can also be used together and a reducing agent to make it a redox type.

These radical polymerization initiators can be used individually or in mixture of 2 or more types.                     

The copolymer [A] obtained in this manner is used for the production of the radiation-sensitive resin composition as it is, or may be separated from the solution and used for the preparation of the radiation-sensitive resin composition.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") by gel permeation chromatography (GPC) of the copolymer [A] is usually in the range of 2,000 to 100,000, preferably in the range of 5,000 to 50,000. In this case, when Mw is less than 2,000, developability, residual film ratio, etc. of a film obtained may fall, or pattern shape, heat resistance, etc. may be impaired, and when it exceeds 100,000, resolution may fall or pattern shape may be damaged. .

Polymeric compounds [B]

Component [B] used in the present invention is a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as "polymerizable compound [B]").

Although a polymeric compound [B] is not specifically limited, Monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid esters are preferable at the point from which polymerization property is favorable and the spacer strength obtained improves, especially trifunctional or more ( Meta) acrylic acid esters are preferable.

As said monofunctional (meth) acrylic acid ester, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate , Isoboroyl acrylate, isoboroyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 2- Methacryloyloxyethyl-2-hydroxypropyl phthalate etc. are mentioned, Furthermore, As a commercial item, For example, Alonics M-11, Copper M-111, Copper M-114 (made by Toagosei Co., Ltd.); KAYARAD TC-110S, TC-120S (manufactured by Nihon Kayaku Co., Ltd.); Biscoat 158, copper 2311 (manufactured by Osaka Yuki Chemical Co., Ltd.), and the like.

Moreover, as said bifunctional (meth) acrylic acid ester, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacryl Tetraethylene glycol dimethacrylate, 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, 1,9-nonanedioldiacrylate, 1,9-nonanedioldimethacrylate Bisphenoxy ethanol fluorene diacrylate, bisphenoxy ethanol fluorene dimethacrylate, etc. are mentioned, Also as a commercial item, it is Alonics M-210, copper M-240, copper M. -6200 (manufactured by Toa Kosei Co., Ltd.), KAYARAD HDDA, East HX-220, East R-604 (manufactured by Nihon Kayaku Co., Ltd.), Biscot 260, East 312, East 335 HP (Osaka Yuki Kagaku High School) Note) manufacture) etc. are mentioned.

Moreover, as said trifunctional or more (meth) acrylic acid ester, For example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, penta Erythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri ( 2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, etc. are mentioned, As a commercial item, for example, Alonics M-309, Copper M-400, Copper M-405 , M-450, M-7100, M-8030, M-8060, TO-1450 (manufactured by Toa Kosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA-60, east DPCA-120 (Nihon Kayaku ( Co., Ltd.), biscoat 295, copper 300, copper 360, copper GPT, copper 3PA, copper 400 (manufactured by Osaka Yuka Kagaku Kogyo Co., Ltd.).

These monofunctional, bifunctional or trifunctional or more (meth) acrylic acid esters can be used individually or in combination of 2 or more types.

In the present invention, the amount of the polymerizable compound [B] is used per 100 parts by weight of the copolymer [A], preferably 50 to 200 parts by weight, more preferably 70 to 140 parts by weight, particularly preferably 80 to 120 parts by weight. to be. In the usage-amount of this range, it is easy to control the film thickness of the spacer obtained, and it can be set as the radiation sensitive resin composition which provides the spacer excellent in strength and adhesiveness.

Photoinitiator [C]

In the present invention, the photopolymerization initiator is to generate an active kind capable of initiating the polymerization of the polymerizable compound [B] by exposure to visible light, ultraviolet rays, far ultraviolet rays, charged particle beams, X-rays, and the like. It contains trihalomethyl triazine represented by.                     

<Formula 1>

In the formula, X represents a halogen,

A represents a group represented by CX ₃ or the following formula,

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

Examples of the trihalomethyltriazines represented by the general formula (1) include 2,4,6-tris (trichloromethyl) -s-triazine and 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 (trichloro Methyl) -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-tria Gin, 2- (2-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -4,6-bis (trichloro Rhomethyl) -s-triazine, 2- (3-methoxy-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxy-β-sty Reyl) -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, represented by the following formula (2) Compounds and the like.                     

In the formula, X represents a halogen atom, and examples of these halogen atoms 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, and an alkyl tea having 1 to 10 carbon atoms. An aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a di (alkyl having 1 to 10 carbon atoms) amino group, a di (aryl having 6 to 10 carbon atoms) amino group, An alkylcarbonyl group having 2 to 11 carbon atoms, an arylcarbonyl group having 7 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkylcarbonyloxy group having 2 to 10 carbon atoms,

R ² and R ³ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms,

i is an integer from 1 to 4.

As a halogen atom of R <^1> , R <^4> and R <^5> , a fluorine, chlorine, bromine is mentioned, for example.

Here, examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and the like. These may be straight or branched chains.

Examples of the alkoxyl group having 1 to 10 carbon atoms and the alkylthio group having 1 to 10 carbon atoms include a group corresponding to an alkyl group exemplified for the alkyl group having 1 to 10 carbon atoms, for example, a methoxy group and a methylthio group. Can be mentioned.

Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, naphthyl and the like.

As the aryloxy group having 6 to 10 carbon atoms and the arylthio group having 6 to 10 carbon atoms, examples of the aryl group having 6 to 10 carbon atoms include a group corresponding to the aryl group exemplified, for example, a phenoxy group and a phenylthio group. It can be mentioned as.

As a di (C1-C10 alkyl) amino group, the group corresponded to having the alkyl group illustrated with respect to the C1-C10 alkyl group, for example, a di (methyl) amino group etc. are mentioned as a specific example. In this case, the two alkyl groups may be the same or different.

As a di (C6-C10 aryl) amino group, the group corresponded to having an aryl group illustrated with respect to a C6-C10 aryl group, for example, a di (phenyl) amino group etc. are mentioned as a specific example. In this case, the two aryl groups can be the same or different.

Examples of the alkylcarbonyl group having 2 to 11 carbon atoms include groups corresponding to those having an 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. For example.                     

Examples of the arylcarbonyl group having 7 to 11 carbon atoms include groups corresponding to those having an aryl group exemplified for the aryl group having 6 to 10 carbon atoms, for example, a phenylcarbonyl group.

Examples of the alkoxycarbonyl group having 2 to 10 carbon atoms and the alkylcarbonyloxy group having 2 to 10 carbon atoms include groups corresponding to those having an alkyl group exemplified for an alkyl group having 1 to 10 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, and the like. A methylcarbonyloxy group, an ethylcarbonyloxy group, etc. are mentioned as a specific example.

Of these trihalomethyltriazines, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6- Bis (trichloromethyl) -s-triazine and the compound represented by the formula (2) are preferably used.

As preferable trihalomethyl triazines represented by the said Formula (2), it is 2- (4-diethylamino-2-methyl- (beta) -styryl) -4,6-bis (trichloromethyl) -s-, for example. 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 (trichloro Methyl) -s-triazine, 2- (4-dimethylamino-2-cyano-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-diethyl Amino-4-methylthio-β-styryl) -4,6-bis (trichloromethyl) -s-triazine and the like.

Among 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 (trichloro Romethyl) -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]. By using within this range, the radiation sensitive resin composition excellent in the balance of the heat resistance of solvent and solvent resistance, and the controllability of the pattern shape after image development is provided.

Photoinitiator [C] can be used in combination with another photoinitiator as needed.

Such other photoinitiators include, for example, α-diketones such as benzyl and diacetyl; Acyloins, such as benzoin, o-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- [4- Acetophenones, such as (methylthio) phenyl] -2-morpholino-1-propaneone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; Quinones such as anthraquinone and 1,4-naphthoquinone; Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide; Peroxides, such as benzoyl peroxide and di-t- butyl peroxide, etc. are mentioned.                     

In addition, as a commercial item of another photoinitiator, IRGACURE-184, 369, 500, 651, 907, 819, 1700, Darocur-1173, 1116, 2959, 1664, 4043, etc. (Chiba Specialty Chemicals Co., Ltd.), KAYACURE-DETX, East MBP, East DMBI, East EPA, East OA (manufactured by Nihon Kayaku Co., Ltd.), VICURE-10, East 55 (manufactured by STAUFFER Co. LTD.), TRIGONALP1 ( AKZO Co. LTD), SANDORAY 1000 (manufactured by SANDOZ Co. LTD), DEAP (manufactured by APJOHN Co. LTD), QUANTACURE-PDO, East ITX, East EPD (manufactured by WARD BLEKINSOP Co. LTD) Can be.

In this invention, by using these other photoinitiators together with photoinitiator [C], it becomes possible to further improve the compressive strength of a spacer, adhesiveness with a board | substrate, etc., and to control the cross-sectional shape of a pattern.

The said other photoinitiator can be used individually or in mixture of 2 or more types.

The use ratio of another photoinitiator is 100 weight part or less with respect to 100 weight part of photoinitiators [C], More preferably, it is 50 weight part or less, Especially preferably, it is 30 weight part or less. In this case, when the use ratio of another photoinitiator exceeds 100 weight part, there exists a possibility that the magnitude | size of the pattern obtained may become too large beyond the allowable range rather than the design size of a mask pattern.

In addition, a photoinitiator [C] can also improve a sensitivity further by using together with a sensitizer in presence or absence of another photoinitiator.

Examples of the sensitizer include N-methyldiethanolamine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, p -Dimethylaminobenzoic acid i-amyl, 2, 4- diethyl thioxanthone, thioxanthone-4-sulfonic acid, etc. are mentioned.

Among these sensitizers, 4,4'-bis (diethylamino) benzophenone, 2,4-diethyl thioxanthone and the like are preferable.

The said sensitizer can be used individually or in mixture of 2 or more types.

The use ratio of the sensitizer is preferably 40 parts by weight or less, and more preferably 20 parts by weight or less based on 100 parts by weight of the photopolymerization initiator [C]. In this case, when the use ratio of the said sensitizer exceeds 40 weight part, there exists a tendency for developing waste to occur easily.

Other additives

The radiation sensitive resin composition of this invention can contain additives other than the said component as needed in the range which does not impair the desired effect of this invention.

The additives include a surfactant for improving the coatability.

As a commercial item of the said surfactant, for example, BM-1000, BM-1100 (made by BM CHEMIE company), Megapack F142D, copper F172, copper F173, copper F183 (made by Dai Nippon Ink Chemical Industries, Ltd.), flow Ride FC-135, East FC-170C, East FC-430, East FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Supron S-112, East S-113, East S-131, East S-141, East S-145, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (Asahi Glass Co., Ltd.), F-Top EF301, copper 303, copper 352 (manufactured by Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (Toray Silicon Co., Ltd.) Fluorine-based or silicone-based surfactants such as ()).

Moreover, as surfactant other than the said commercial item, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxy ethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; Nonionic surfactants, such as polyoxyethylene dialkyl esters, such as polyoxyethylene dilaurate and polyoxyethylene distearate, and KP341 (made by Shin-Etsu Chemical Co., Ltd.), polyflow No. as a commercial item .57, 95 (made by Kyoeisha Chemical Co., Ltd.), etc. are mentioned.

These surfactant can be used individually or in mixture of 2 or more types.

The compounding quantity of surfactant is the range of 5 weight part or less, More preferably, it is 2 weight part or less with respect to 100 weight part of copolymers [A]. In this case, when the compounding quantity of surfactant exceeds 5 weight part, film roughness will arise easily at the time of application | coating.

In addition, in order to improve the adhesiveness with the base, an adhesive aid can be used.

As said adhesion | attachment adjuvant, a functional silane coupling agent is preferable, The silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is mentioned, More specifically, a trimethoxysilyl benzoic acid , γ-methacrylooxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3 ' And 4'-epoxycyclohexyl) ethyltrimethoxysilane.

These adhesion aids can be used individually or in mixture of 2 or more types.                     

The blending 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, when the compounding quantity of an adhesion | attachment adjuvant exceeds 20 weight part, there exists a tendency for image development waste to occur easily.

Radiation-sensitive resin composition

The radiation sensitive resin composition of this invention is prepared by mixing uniformly the structural component containing a copolymer [A], a polymeric compound [B], a photoinitiator [C], and the other additive added arbitrarily.

When preparing a radiation sensitive resin composition, a suitable solvent is added normally and it is set as a composition solution.

As a solvent used for preparation of a radiation sensitive resin composition solution, the thing which melt | dissolves each component which comprises a radiation sensitive resin composition uniformly and does not react with each component further is used, For example, copolymer [A] The same thing as the solvent illustrated about the superposition | polymerization which manufactures is mentioned.

Among these solvents, ethylene glycol monoalkyl ethers, ethylene glycol monoalkyl ether acetates, diethylene glycol alkyl ethers, and propylene glycol mono, in terms of dissolving ability of each component, reactivity with each component, and ease of forming a coating film. Alkyl ether acetates, alkyl alkoxypropionates, etc. are preferable.

The said solvent can be used individually or in mixture of 2 or more types.

Moreover, in preparation of a radiation sensitive resin composition solution, you may use together a high boiling point solvent simultaneously with the said solvent.                     

As the high boiling point solvent, for example, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone , Dimethyl sulfoxide, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, capuronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, oxalic acid di Ethyl, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, and the like.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

The composition solution prepared as described above may be used, if necessary, by filtering with a Millipore filter having a pore size of, for example, about 0.2 to 0.5 μm.

Formation of spacers for display panels

The radiation sensitive resin composition of this invention is especially suitable as a material for forming the spacer for display panels, such as a liquid crystal panel or a touch panel.

The formation method of the display panel spacer of this invention is characterized by including the following processes.

① Process of forming the coating film of said radiation sensitive resin composition on a board | substrate.

② A step of irradiating at least a portion of the coating film with radiation.

③ developing process.

④ heat treatment process.

Hereinafter, each process mentioned above is demonstrated.

① Process of forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate

When forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate, after apply | coating a composition solution to the surface of a board | substrate, it can carry out by prebaking and removing a solvent.

As a coating method of a composition solution, various methods, such as a spray method, a roll coating method, and a spin coating method, can be used, for example.

In addition, although the conditions of prebaking differ also with kinds, compounding ratio, etc. of each structural component, it is about 1 to 15 minutes at 70-90 degreeC normally.

② a step of irradiating at least a portion of the coating film with radiation

Subsequently, the coating film formed as described above is exposed and polymerized through a mask of a predetermined pattern, and then developed by a developing solution to remove unnecessary portions to form a pattern.

As radiation used for exposure, visible rays, ultraviolet rays, far ultraviolet rays, charged particle beams, X rays, and the like can be appropriately selected, but ultraviolet rays are preferred.

③ Development process

As a developing method, it can be any of adhesion method, immersion method, and a shower method, for example, and developing time is normally 30 to 180 second.

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; Tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine and triethylamine; Tertiary alkanol amines such as dimethylethanol amine, methyldiethanolamine and triethanolamine; Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Alicyclic tertiary amines such as -5-nonane; Aromatic tertiary amines such as pyridine, coridine, lutidine and quinoline; Aqueous solutions of alkaline compounds, such as quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant may be added to the aqueous solution of the alkaline compound.

After development, it wash | cleans for 30 to 90 second, for example by running water etc., and removes an unnecessary part, and a predetermined pattern is formed by drying compressed air and compressed nitrogen.

④ heat treatment process

Thereafter, the pattern is heated for a predetermined time at a predetermined temperature, for example, 150 to 250 DEG C, for 5 to 30 minutes on a hot plate, for example, for 30 to 90 minutes in an oven, using a heating device such as a hot plate or an oven. By heating, the desired spacer can be obtained.

Display panel

The display panel of this invention has the spacer formed as mentioned above with respect to the radiation sensitive resin composition of this invention.

As such a display panel, a liquid crystal display panel, a touch panel, etc. are mentioned.                     

Although an Example and a comparative example demonstrate this invention further more concretely below, this invention is not limited to these Examples.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of diethylene glycol methylethyl ether, 20 parts by weight of methacrylic acid, meta 45 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, and 25 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate were replaced with nitrogen, and the temperature of the solution was gradually reduced to 70 ° C. And the polymerization was carried out while maintaining the temperature for 5 hours to obtain a solution of copolymer [A-1].

Solid content concentration of this solution was 33.2 weight%, and Mw of the copolymer [A-1] was 24,000.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of diethylene glycol methylethyl ether, 20 parts by weight of methacrylic acid, meta 50 parts by weight of glycidyl methacrylate and 25 parts by weight of styrene were added thereto, followed by nitrogen replacement. Then, 5 parts by weight of 1,3-butadiene was added thereto, and the temperature of the solution was gradually increased to 70 ° C. while maintaining the temperature for 5 hours. It superposed | polymerized and obtained the solution of copolymer [A-2].

Solid content concentration of this solution was 33.3 weight%, and Mw of the copolymer [A-2] was 20,000.                     

<Example 1>

Preparation of a radiation sensitive resin composition

100 parts by weight (solid content) of the solution of the copolymer [A-1] obtained in Synthesis Example 1, 80 parts by weight of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as the polymerizable compound [B]; 8 parts by weight of 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine as the photopolymerization initiator [C] so that the solid content concentration is 35% by weight propylene glycol monomethyl ether acetate After dissolving in, it filtered by the Millipore filter of 0.2 micrometer of pore diameters, and produced the composition solution (S-1).

Formation of spacers

After apply | coating composition solution (S-1) using a spinner on a glass substrate, it prebaked for 3 minutes at 80 degreeC on the hotplate, and formed the coating film.

Subsequently, the obtained coating film was made into 100 micrometers of exposure gaps in the air using the mask (10 micrometer x 10 micrometers) of a predetermined pattern, and the exposure intensity of the ultraviolet-ray of 100 W / m <^2> exposure intensity in wavelength 365nm is carried out. Was performed for 30 seconds. Then, it developed by 0.2 weight% of tetramethylammonium hydroxide aqueous solution at 25 degreeC for 1 minute, removed the unnecessary part, and wash | cleaned for 1 minute with pure water, and obtained the pattern.

Subsequently, the obtained pattern was heated in an oven for 60 minutes at 220 degreeC, and the spacer of 5 micrometers in height which has a predetermined pattern was obtained.

evaluation

The following items were evaluated about the obtained spacer. The evaluation results are shown in Table 1.

(1) Dimensions of pattern bottom section (width)

It was measured by a scanning electron microscope.

(2) spacer strength

It evaluated as follows using the micro compression tester (MCTM-200, the Shimadzu Corporation make).

Breaking load (measured temperature: 25 ° C.); With respect to the spacer, a compressive load in the vertical direction was applied at a constant speed (2.65 mN / sec) by a planar indenter having a diameter of 50 µm, and the load when cracks or fractures occurred in the spacer was measured to be a breakdown load.

Fracture distortion (measured temperature: 25 ° C.); The value obtained by subtracting the compression displacement at the time of reaching the breaking load from the height (5 μm) of the spacer was defined as the breaking distortion.

(3) heat resistance

The dimensional change rate of the pattern height when the spacer was heated at 240 degreeC for 60 minutes in oven was calculated | required.

<Example 2>

A composition solution (S-2) was produced in the same manner as in Example 1 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]. , Spacers were formed and evaluated.

The evaluation results are shown in Table 1.                     

<Example 3>

5 parts by weight of 2- (4-diethylamino-2-methyl-β-styryl) -4,6-bis (trichloromethyl) -s-triazine as the photopolymerization initiator [C] and bis (2,4 A composition solution (S-3) was prepared in the same manner as in Example 1 except that 10 parts by weight of 6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE-819) was used to form and evaluate a spacer.

The evaluation results are shown in Table 1.

<Example 4>

As a photoinitiator [C], 2- (4-diethylamino-2-methyl-β-styryl) -4,6-bis (trichloromethyl) -s-triazine was substituted for 8 parts by weight, and 2- ( Composition solution (S-) in the same manner as in Example 1 except that 10 parts by weight of 4-isobutylamino-2-methyl-β-styryl) -4,6-bis (trichloromethyl) -s-triazine was used. 4) was prepared to form and evaluate spacers.

The evaluation results are shown in Table 1.

Pattern Dimensions (Width) (μm) Breaking load (gf) Fracture Distortion (%) Heat Strain (%) Example 1 10.5 12.0 55 3 Example 2 10.4 11.6 53 4 Example 3 10.3 13.3 57 2 Example 4 10.5 12.6 55 3

According to the present invention, a radiation sensitive resin composition capable of faithfully reproducing the design size of a mask pattern even by proximity exposure and forming a spacer for a display panel excellent in strength, heat resistance, and the like required as a spacer, and obtained therefrom A display panel spacer and a display panel having the spacer are provided.

Claims (7)

(A) a copolymer of (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride with (a2) an epoxy group-containing ethylenically unsaturated compound and (a3) another ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] A radiation-sensitive resin composition containing a photopolymerization initiator containing trihalomethyltriazines represented by the following formula (1), for forming a spacer for a display panel. <Formula 1>

In the formula, X represents a halogen, A represents a group represented by CX ₃ or the following formula,

Here, B, D and E are each independently hydrogen, alkyl group having 1 to 10 carbon atoms, aryl group or alkoxy group, aryloxy group, thioalkyl group, thioaryl group, halogen, cyano group, nitro group, di An alkyl) amino group of 10, a carboxyl group, a hydroxyl group, a ketoalkyl group or a ketoaryl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms or an alkylcarbonyloxy group, and m represents an integer of 1 to 5. [C] The radiation sensitive resin composition according to claim 1, wherein the compound represented by the formula [1] is a trihalomethyl triazine represented by the following formula (2). <Formula 2>

In the formula, X represents a halogen atom, 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, and a C 1 to 10 An alkoxyl group, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a di (alkyl having 1 to 10 carbon atoms) amino group, di (Aryl having 6 to 10 carbon atoms) an amino group, an alkylcarbonyl group having 2 to 11 carbon atoms, an arylcarbonyl group having 7 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms or an alkylcarbonyloxy group having 2 to 10 carbon atoms, and represents R ² and R ³ is each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and i is an integer of 1 to 4; The component according to claim 1 or 2, wherein the component [A] is Methacrylic acid / methacrylate glycidyl / styrene / 1,3-butadiene copolymer, Methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer, Methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer, Methacrylic acid / glycidyl acrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer, A radiation sensitive resin composition characterized in that it is at least one selected from acrylic acid / glycidyl acrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene / 1,3-butadiene copolymer. . delete At least ① process of forming the coating film of the radiation sensitive resin composition of Claim 1 or 2 on a board | substrate, ② a step of irradiating at least a portion of the coating film with radiation, ③ developing process, ④ heat treatment process Method for forming a spacer for a display panel comprising a. The display panel spacer formed from the radiation sensitive resin composition of Claim 1 or 2. The display panel which has a display panel spacer formed from the radiation sensitive resin composition of Claim 1 or 2.