JP2002303976A - Radiation sensitive composition, spacer and color liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive composition which gives a cured body having satisfactory strength and excellent adhesion to a substrate and which is used for forming spacers on the driving substrate of a thin film transistor(TFT) system color liquid crystal display. SOLUTION: The radiation sensitive composition contains (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator. The total extent of deformation of a cured body obtained from the composition in the measurement of indentation hardness at 25 deg.C and that at 180 deg.C are <2 μm each.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive composition used for forming a spacer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, and a thin film transistor (TFT) formed therefrom.
The present invention relates to a spacer for a color liquid crystal display device, and a thin film transistor (TFT) color liquid crystal display device including the spacer.

[0002]

2. Description of the Related Art Conventionally, in a color liquid crystal display device, beads made of silica or polystyrene having a predetermined particle diameter are formed between liquid crystal layers in order to keep a constant distance (cell gap) between two substrates. It was sprayed randomly over the entire panel. However, according to such a method, there are problems that the dispersed density of the dispersed beads is not uniform depending on the location, which causes display unevenness, and that the contrast is reduced due to light scattering of the backlight by the beads.
Therefore, a method of forming a spacer by photolithography, for example, applying a radiation-sensitive composition to a substrate,
A method of forming a spacer having a predetermined shape by exposing through a predetermined mask and then developing the same has been proposed. According to this method, the spacer can be selectively formed in a place other than the effective pixel portion, and the above problem can be solved. Further, according to this method, since the cell gap can be controlled by the thickness of the coating film formed from the radiation-sensitive composition, the cell gap can be easily controlled and the accuracy is high.

By the way, a thin film transistor (TFT)
Conventionally, in a color liquid crystal display device using a driving substrate on which a color filter is provided, a color filter substrate for displaying a color image is manufactured separately from the driving substrate on which a thin film transistor (TFT) is disposed. The filter substrate is manufactured by laminating the driving substrate. However, in this method, since the accuracy of the alignment at the time of bonding is low, it is necessary to increase the width of the black matrix, and it is difficult to increase the aperture ratio (that is, the ratio of the aperture through which light passes). There was a disadvantage that it was. On the other hand, in contrast to the above method, a colored layer is formed directly or via a passivation film such as a silicon nitride film on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and the colored layer is formed. Substrate is made of ITO (tin-doped indium oxide) by sputtering
A method was developed in which the substrate was bonded to a substrate on which electrodes were formed. In this method, since a colored layer including pixels and a black matrix is formed directly on the driving substrate, a bonding step between the color filter substrate and the driving substrate is not required, and the aperture ratio is smaller than the former method. Is significantly improved, and a bright and high-definition display device is obtained.

The spacer used in the latter method is generally formed from a radiation-sensitive composition by the above-described photolithography. However, the latter type of color liquid crystal display device requires stricter dimensional accuracy than the conventional color liquid crystal display device,
Even a slight gap unevenness causes display failure. And
Even if a spacer is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed using a conventionally used radiation-sensitive composition, the spacer does not have sufficient strength. When assembling, it may be plastically deformed or broken, and there is a problem in that the yield of products is reduced. Therefore, a radiation-sensitive composition for forming a spacer on the surface of a driving substrate on which a thin film transistor (TFT) is arranged, which has a cured product having sufficient strength and excellent adhesion to a substrate, is required. However, a satisfactory composition has not yet been found.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a thin film transistor (TFT) in which a cured product has a sufficient strength and excellent adhesion to a substrate. Radiation-Sensitive Composition Used to Form a Spacer on a Driving Substrate of a Color Liquid Crystal Display, a Spacer for a Thin Film Transistor (TFT), and a Thin Film Transistor (TFT) Having the Spacer Another object of the present invention is to provide a color liquid crystal display device.

[0006]

According to the present invention, the above-mentioned problems are firstly solved by (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization. A driving substrate for a thin film transistor (TFT) type color liquid crystal display device, comprising a radiation-sensitive composition containing an initiator, wherein a cured product obtained from the composition has an indentation hardness at 25 ° C. of 2 μm or less. This is achieved by a radiation-sensitive composition used to form a spacer thereon.

Further, according to the present invention, the above-mentioned problems are secondly caused by (A) a colorant, (B) an alkali-soluble resin, and (C)
A radiation-sensitive composition containing a polyfunctional monomer and (D) a photopolymerization initiator, and one of the effects obtained therefrom.
A radiation-sensitive composition used for forming a spacer on a driving substrate of a thin film transistor (TFT) color liquid crystal display device, wherein the indentation hardness at 80 ° C. is within 2.5 μm. Is done.

Further, according to the present invention, the above-mentioned object is achieved, thirdly, by a spacer for a thin film transistor (TFT) type color liquid crystal display device formed from each of the above-mentioned radiation-sensitive compositions.

Further, according to the present invention, fourthly, the above object is achieved by a thin film transistor (TFT) type color liquid crystal display device including the spacer. The term “radiation” as used in the present invention refers to those including visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays and the like.

Hereinafter, the present invention will be described in detail. (A) Colorant The colorant in the present invention is not particularly limited in color tone, and may be any of a pigment, a dye, and a natural pigment. Preferably, a pigment, particularly preferably an organic pigment and / or carbon black is used. As the organic pigment, for example, compounds classified as Pigment in a color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (CI) numbers are given. Can be mentioned.

CI Pigment Yellow 83, CI Pigment Yellow 128, CI Pigment Yellow 138,
CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153,
CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168,
CI Pigment Yellow 175, CI Pigment Yellow 185; CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 3
8;

CI Pigment Red 177, CI Pigment Red 202, CI Pigment Red 206, CI
Pigment Red 207, CI Pigment Red 20
8, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242,
CI Pigment Red 243, CI Pigment Red 2
45, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 265; CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15:
4, CI Pigment Blue 15: 6, CI Pigment Blue 60; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Black 1, CI Pigment Black 7. These organic pigments can be used alone or
A mixture of more than one species can be used. The organic pigment can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, and blue blue. Green, chrome oxide, cobalt green,
Amber, titanium black, synthetic iron black, carbon black and the like can be mentioned. These inorganic pigments can be used alone or in combination of two or more.

Specific examples of the carbon black include:
SAF, SAF-HS, ISAF, ISAF-LS, I
SAF-HS, HAF, HAF-LS, HAF-HS,
NAF, FEF, FEF-HS, SRF, SRF-L
M, SRF-LS, GPF, ECF, N-339, N-
Furnace black such as 351; thermal black such as FT and MT; and acetylene black. These carbon blacks can be used alone or in combination of two or more.

In the present invention, each of the above pigments can be used after modifying its particle surface with a polymer, if desired. As a polymer that modifies the pigment particle surface,
Examples thereof include polymers described in JP-A-8-259876 and various commercially available polymers or oligomers for dispersing pigments.

The coloring agent of the present invention can be used together with a dispersant, if desired. Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ether, polyoxyethylene n- Polyoxyethylene alkyl phenyl ethers such as nonyl phenyl ether;
In addition to polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; polyethylene imines; Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.)
), F-Top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.), Florard (manufactured by Sumitomo 3M Limited), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.) , Disperbyk-1
01, 103, 107, 110, 111, 1
15, 130, 160, 161, 162, 1
63, 164, 165, 166, 170, 1
80, 182, 2000, 2001 (all manufactured by Big Chemie Japan KK), Solsperse S500
0, S12000, S13240, S1394
0, S17000, S20000, S2200
0, S24000, S24000GR, S260
EFKA46, 47, 48, 74
5, 4540, 4550, 6750, EFKA
LP4008, 4009, 4010, 4015,
4050, 4055, 4560, 4800, E
FKA Polymer 400, 401, 402,
403, 450, 451, and 453 (all manufactured by Efka Chemicals Co., Ltd.) and the like. These surfactants can be used alone or in combination of two or more. The amount of the surfactant used is the coloring agent 1
It is usually 50 parts by weight or less, preferably 0 to 30 parts by weight, based on 00 parts by weight.

(B) Alkali-Soluble Resin As the alkali-soluble resin in the present invention, (A) a developer which acts as a binder with respect to a colorant and is used in a developing step in producing a spacer, especially Although it is not particularly limited as long as it is soluble in an alkali developing solution, an alkali-soluble resin having a carboxyl group is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups. Monomer (hereinafter referred to as “carboxyl group-containing unsaturated monomer”) and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as “copolymerizable unsaturated monomer”).
(Hereinafter referred to as “carboxyl group-containing copolymer”)
That. Is preferred.

Examples of the unsaturated monomer having a carboxyl group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid and the like. Unsaturated dicarboxylic acids such as acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid or anhydrides thereof; trivalent or higher unsaturated polycarboxylic acid or anhydride thereof; succinic acid mono ( 2-acryloyloxyethyl),
Mono-((meta) of di- or higher-valent polycarboxylic acids such as mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, and mono (2-methacryloyloxyethyl) phthalate ) Acryloyloxyalkyl] esters; and mono (meth) acrylates of polymers having carboxy groups and hydroxyl groups at both terminals such as ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . Of these carboxyl group-containing unsaturated monomers, mono (2-acryloyloxyethyl) succinate and mono (2-acryloyloxyethyl) phthalate are M-5300 and M-5400 (Toagosei Co., Ltd., respectively) Co., Ltd.). The unsaturated monomers containing a carboxyl group can be used alone or in combination of two or more.

Examples of the copolymerizable unsaturated monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene and p-vinyltoluene.
Chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 2-vinylbenzyl methyl ether, 3-vinylbenzyl methyl ether,
Aromatic vinyl compounds such as 4-vinylbenzyl methyl ether, 2-vinylbenzyl glycidyl ether, 3-vinylbenzyl glycidyl ether and 4-vinylbenzyl glycidyl ether; indenes such as indene and 1-methylindene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-
Propyl acrylate, n-propyl methacrylate,
i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate,
3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2- Methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2
-Phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxy Dipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, tricyclo [5.2.1.0
^2,6 ] decane-8-yl acrylate, tricyclo [
5.2.1.0 ^2,6 ] unsaturated carboxylic acids such as decane-8-yl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate Acid esters;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; unsaturated such as glycidyl acrylate and glycidyl methacrylate Carboxylic acid glycidyl esters; vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide Amides such as N, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; maleimide, N
Unsaturated imides such as -phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly And macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of a polymer molecular chain such as -n-butyl methacrylate and polysiloxane. These copolymerizable unsaturated monomers can be used alone or in combination of two or more.

The carboxyl group-containing copolymer of the present invention contains acrylic acid and / or methacrylic acid as an essential component, and in some cases, mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyl succinate). Loxyethyl), at least one member selected from the group consisting of ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.
Carboxyl group-containing unsaturated monomer component further containing a kind of compound, styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, Copolymer with at least one selected from the group consisting of glycerol monomethacrylate, glycerol monoacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer (hereinafter referred to as “carboxyl group-containing copolymer (α)”) Is preferred.

Specific examples of the carboxyl group-containing copolymer (α) include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, ) Acrylic acid / 2-
Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate Macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth)
Acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acryl Acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Mono [2- (meth) acryloyloxyethyl succinate] / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / mono [2- (meth) acryloyloxy succinate) Ethyl] / Still / Allyl (meth) acrylate /
N-phenylmaleimide copolymer (meth) acrylic acid /
Styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycacrolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol Mono (meth) acrylate / N-phenylmaleimide copolymer and the like can be mentioned.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5
５０50% by weight, preferably 10-40% by weight. In this case, when the copolymerization ratio is less than 5% by weight, the solubility of the obtained radiation-sensitive composition in an alkali developing solution tends to decrease, while when it exceeds 50% by weight, the solubility in an alkali developing solution becomes poor. When the spacer layer is developed with an alkali developer, the spacer layer tends to fall off from the substrate and the spacer surface tends to be rough.

The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) of the alkali-soluble resin measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is usually 3,000 to 3.
00,000, preferably 5,000-100,000
It is. Further, the number average molecular weight (hereinafter, referred to as “Mn”) in terms of polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin is usually 3,000-6.
0,000, preferably 5,000 to 25,000. In the present invention, such specific Mw and M
By using an alkali-soluble resin having n, a radiation-sensitive composition excellent in developability can be obtained, whereby a spacer pattern having a sharp pattern edge can be formed, and an unexposed portion during development can be obtained. Residue, background dirt, film residue and the like hardly occur on the substrate and the light shielding layer. The ratio of Mw to Mn (Mw / Mn) of the alkali-soluble resin is usually 1 to 5, preferably 1 to 4.

In the present invention, the alkali-soluble resin is
They can be used alone or in combination of two or more. The amount of the alkali-soluble resin used in the present invention is
(A) Usually, 10 to 1, based on 100 parts by weight of the coloring agent.
000 parts by weight, preferably 20 to 500 parts by weight.
In this case, if the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, alkali developability may be reduced, and background contamination or film residue may be generated on the unexposed portion of the substrate or the light-shielding layer. If the amount exceeds 1,000 parts by weight, the concentration of the colorant relatively decreases, so that it may be difficult to achieve the desired color density as a thin film.

(C) Polyfunctional Monomer The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds. Examples of polyfunctional monomers include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol; diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycerin, trimethylol Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as propane, pentaerythritol and dipentaerythritol, and their dicarboxylic acid modified products; polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins, spirane resins, etc. Oligoacrylates or oligomethacrylates; hydroxy-terminated poly-1,3-butadiene, hydroxy-terminated polyisoprene, hydroxy-terminated Diacrylates or dimethacrylates and the both ends hydroxylated polymer re caprolactone, tris (2-
Acryloyloxyethyl) phosphate, tris (2-
(Methacryloyloxyethyl) phosphate and the like.

Among these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols and modified products of dicarboxylic acids thereof, specifically, trimethylolpropane triacrylate, trimethylolpropane Trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, the following formula ( 1)

[0029]

Embedded image

A compound represented by the following formula (2)

[0031]

Embedded image

The compounds represented by the following formulas are preferred. In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate are excellent in the strength and surface smoothness of the colored layer and on the unexposed part of the substrate. In addition, it is preferable in that background contamination, film residue and the like hardly occur on the light shielding layer.

In the present invention, the polyfunctional monomers can be used alone or as a mixture of two or more. The amount of the polyfunctional monomer used in the present invention is usually 5 to 500 parts by weight based on 100 parts by weight of the alkali-soluble resin (B).
Parts by weight, preferably 30 to 300 parts by weight. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the spacer tend to decrease, while if it exceeds 500 parts by weight, for example, alkali developability decreases. In addition, background contamination, film residue, and the like tend to easily occur on the unexposed portion of the substrate or the light-shielding layer.

In the present invention, a part of the polyfunctional monomer may be replaced with a monofunctional monomer having one polymerizable unsaturated bond. Examples of the monofunctional monomer include the same monomers as the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer exemplified for the alkali-soluble resin (B), and N-acryloyl morpholine. In addition to phosphorus, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, commercially available products such as M-5300, M-5400, and M-5600
(Trade name, manufactured by Toagosei Co., Ltd.) and the like. These monofunctional monomers can be used alone or in combination of two or more.

The proportion of the monofunctional monomer is usually 90 to the total amount of the polyfunctional monomer and the monofunctional monomer.
% By weight, preferably 0 to 50% by weight. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the obtained spacer may be insufficient. The total amount of the polyfunctional monomer and the monofunctional monomer used in the present invention is usually 5 to 500 parts by weight, preferably 30 to 500 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B). 300 parts by weight. In this case, if the total amount is less than 5 parts by weight, the strength and surface smoothness of the spacer tend to decrease, while if it exceeds 500 parts by weight, for example, the alkali developability decreases or the unexposed portion Background dirt, film residue, and the like tend to easily occur on the substrate or the light shielding layer.

(D) Photopolymerization Initiator The photopolymerization initiator of the present invention initiates polymerization of the (C) polyfunctional monomer and optionally used monofunctional monomer by exposure to radiation. It has the action of generating active species that do. Examples of such a photopolymerization initiator include a biimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, an α-diketone compound, a phosphine compound, a polynuclear quinone compound, and a triazine compound. be able to.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,
4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis ( 4-ethoxycarbonylphenyl) -1,2 '
-Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'
-Biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-
1,2′-biimidazole, 2,2′-bis (2,4,
6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'
-Tetraphenyl-1,2'-biimidazole, 2,
2'-bis (2,4,6-tribromophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned.

Specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin i-propyl ether, benzoin i-butyl ether, methyl 2-benzoylbenzoate and the like. Specific examples of the acetophenone-based compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2-hydroxy-2-methyl-1-phenylpropane. -1-one, 1- (4-i-propylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 1-
(4-methylthiophenyl) -2-methyl-2-morpholinopropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-2-hydroxypropan-1-one, 1- (4-morpholinophenyl) -2-benzyl-2-dimethylaminobutane-1-
On, 1-hydroxycyclohexyl phenyl ketone,
2,2-dimethoxy-1,2-diphenylethane-1-
ON etc. can be mentioned.

Specific examples of the benzophenone-based compound include 3,3-dimethyl-4-methoxybenzophenone. Further, specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoyl formate and the like. Further, specific examples of the phosphine-based compound include:
Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2,4,4-trimethylpentylbis (2,6-dimethoxybenzoyl) phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. be able to. Specific examples of the polynuclear quinone-based compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1,4-naphthoquinone.

Further, specific examples of the triazine compound include 2,4,6-tris (trichloromethyl)-
s-Triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-Triazine, 2- [2- (furan-
2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2-
(3,4-dimethoxyphenyl) ethenyl] -4,6-
Bis (trichloromethyl) -s-triazine, 2- (4
-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, the following formula (3)

[0041]

Embedded image (Hereinafter, referred to as “triazine-based compound (3)”), the following formula (4)

[0042]

Embedded image (Hereinafter, referred to as "triazine-based compound (4)"). In the present invention, the photopolymerization initiators can be used alone or in combination of two or more.

The general use amount of the photopolymerization initiator in the present invention is usually based on 100 parts by weight of the total of the polyfunctional monomer (C) and the optionally used monofunctional monomer. ,
The amount is 0.01 to 200 parts by weight, preferably 1 to 120 parts by weight, particularly preferably 1 to 100 parts by weight. In this case, if the total amount is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which spacer patterns are arranged according to a predetermined arrangement. More than
The formed spacers easily fall off from the substrate during development, and background dirt on the unexposed part of the substrate or light-shielding layer,
There is a tendency that film residue or the like is likely to occur.

In the present invention, the spacer is, for example,
A method using a black radiation-sensitive composition [I] described below, a method of laminating three colored layers using three radiation-sensitive compositions [I] of red, green or blue to form a spacer, etc. Although it can be formed, it is desirable to use different types and amounts of the photopolymerization initiator depending on the color tone of the radiation-sensitive composition [I] used. That is, in the case of the red and green radiation-sensitive compositions [I], 1- (4-methylthiophenyl) -2-methyl-2-morpholinopropan-1-one and 1- ( 4-
Acetophenone-based compounds such as morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one;
Triazine compounds such as triazine compound (3) and triazine compound (4) are preferred. The amount of the photopolymerization initiator used is usually 0.01 to 80 parts by weight based on 100 parts by weight of the total of the polyfunctional monomer (C) and the optionally used monofunctional monomer. Parts, preferably 1 to 70 parts by weight.

In the case of the blue radiation-sensitive composition [I], the photopolymerization initiator is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-
Biimidazole compounds such as 1,2'-biimidazole are preferred. The amount of the photopolymerization initiator used is usually 0.01 to 80 parts by weight based on 100 parts by weight of the total of the polyfunctional monomer (C) and the optionally used monofunctional monomer. Parts, preferably 1 to 70 parts by weight.

Further, in the case of the black radiation-sensitive composition [I], 1- (4-methylthiophenyl) -2-methyl-2-morpholinopropane-1 is used as a photopolymerization initiator.
Acetophenone compounds such as -one and 1- (4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5 , 5'-Tetraphenyl-1,2 '
-A biimidazole-based compound such as biimidazole is preferred. The amount of the photopolymerization initiator used is (C) the total of the polyfunctional monomer and the optionally used monofunctional monomer,
With respect to 00 parts by weight, usually 0.01 to 150 parts by weight,
Preferably it is 1 to 130 parts by weight.

-Hydrogen Donor- In the present invention, when a biimidazole compound is used as the photopolymerization initiator, it is preferable to use a hydrogen donor described below in combination, since sensitivity can be improved. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound upon exposure.

As the hydrogen donor, mercaptan compounds and amine compounds defined below are preferable. The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, and more preferably 1 to 2 mercapto groups directly bonded to the mother nucleus (hereinafter, referred to as “ Mercaptan hydrogen donor ”). The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, and more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter, referred to as “ Amine hydrogen donors "
That. ). In addition, these hydrogen donors can have a mercapto group and an amino group simultaneously.

Hereinafter, these hydrogen donors will be described more specifically. The mercaptan-based hydrogen donor can have one or more benzene rings or one or more heterocycles, or can have both a benzene ring and a heterocycle. It may or may not be formed. When the mercaptan-based hydrogen donor has two or more mercapto groups, one or more of the remaining mercapto groups is substituted with an alkyl, aralkyl, or aryl group as long as at least one free mercapto group remains. As long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms It may have structural units linked in the form of disulfides. Further, the mercaptan-based hydrogen donor is a carboxyl group, an alkoxycarbonyl group,
It may be substituted by a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like.

Specific examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole,
Examples thereof include mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, and 2-mercapto-2,5-dimethylaminopyridine. Among these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable,
Particularly, 2-mercaptobenzothiazole is preferable.

The amine-based hydrogen donor can have one or more benzene rings or one or more heterocycles, respectively.
Can have both a benzene ring and a heterocyclic ring,
When having two or more of these rings, a condensed ring may or may not be formed. In the amine hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group, It may be substituted by a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such an amine hydrogen donor include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminoprophenone. Piophenone, ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like can be mentioned. Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferred, and 4,4′-bis (diethylamino) benzophenone is particularly preferred.
-Bis (diethylamino) benzophenone is preferred.
The amine-based hydrogen donor has a function as a sensitizer even in the case of a photopolymerization initiator other than the biimidazole-based compound.

In the present invention, the hydrogen donors can be used alone or as a mixture of two or more. However, one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors are used. It is preferable to use them in combination in that the formed spacer is hardly dropped from the substrate during development, and the strength and sensitivity of the spacer are high. Specific examples of the combination of a mercaptan-based hydrogen donor and an amine-based hydrogen donor include 2-mercaptobenzothiazole /
4,4'-bis (dimethylamino) benzophenone, 2
-Mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4
4'-bis (diethylamino) benzophenone and the like can be mentioned, and more preferable combinations are 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis ( Diethylamino) benzophenone, a particularly preferred combination is 2-mercaptobenzothiazole / 4,4′-bis (diethylamino)
Benzophenone. The weight ratio of the mercaptan hydrogen donor to the amine hydrogen donor in the combination of the mercaptan hydrogen donor and the amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 4. 3.

In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the amount used is based on 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. It is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, if the amount of the hydrogen donor used is less than 0.01 part by weight, the effect of improving sensitivity tends to decrease, while if it exceeds 40 parts by weight, the formed spacer falls off the substrate during development. Tends to be easier.

-Sensitizer- Further, in the present invention, one or more sensitizers can be used in combination with the photopolymerization initiator, if necessary. Although part of the sensitizer is also included in the hydrogen donor, for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, i-amyl 4-dimethylaminobenzoate,
Organic amino compounds such as 4-dimethylaminobenzoic acid and 4-dimethylaminobenzonitrile; and xanthone-based compounds such as diethylthioxanthone and di-i-propylthioxanthone.

Among these sensitizers, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, diethylthioxanthone and di-i-propylthioxanthone are preferred. , 4'-Bis (diethylamino) benzophenone, diethylthioxanthone, di-i-propylthioxanthone and the like are preferable. The sensitizers can be used alone or in combination of two or more.

The amount of the sensitizer used is a total of 100 (C) the polyfunctional monomer and the optionally used monofunctional monomer.
20 parts by weight or less, preferably 1 part by weight,
0 parts by weight or less.

Additives The radiation-sensitive composition of the present invention (hereinafter referred to as "radiation-sensitive composition [I]") may contain various additives as required. As the additive,
An organic acid or an organic amino compound, which further improves the solubility of the radiation-sensitive composition [I] in an alkali developing solution and exhibits an action of further suppressing the remaining undissolved material after development, and the like. .

The organic acid is preferably an aliphatic carboxylic acid having one or more carboxyl groups in the molecule or a phenyl group-containing carboxylic acid. Examples of the aliphatic carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid,
Monocarboxylic acids such as valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, 1,2-
Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
Examples include dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; and tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, and carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon chain. Examples of phenyl group-containing carboxylic acids include aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid and mesitylene acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; trimellitic acid , Trimesic acid, melophanic acid, pyromellitic acid and other trivalent or higher aromatic polycarboxylic acids, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnammylidenic acid , Coumaric acid, umbellic acid and the like.

Of these organic acids, alkali solubility,
As the aliphatic carboxylic acid, aliphatic dicarboxylic acids are preferable, and in particular, malonic acid, adipine, from the viewpoints of solubility in a solvent described below, prevention of background fouling or film residue on the substrate or the light-shielding layer in the unexposed portion. Acid, fumaric acid,
Itaconic acid, citraconic acid, mesaconic acid and the like are preferred.
As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferable, and phthalic acid is particularly preferable. The organic acids can be used alone or in combination of two or more.

The amount of the organic acid is usually at most 15% by weight, preferably at most 10% by weight, based on the whole radiation-sensitive composition [I]. In this case, if the amount of the organic acid used exceeds 15% by weight, the adhesion of the formed spacer to the substrate tends to decrease.

The organic amino compound is preferably an aliphatic amine having at least one amino group in the molecule or a phenyl group-containing amine. Examples of the aliphatic amine include n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-
Butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine,
n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-
Linear, branched or cyclic monoalkylamines such as methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine and 4-ethylcyclohexylamine; methylethylamine, diethylamine, methyl n -Propylamine, ethyl n-propylamine, di-
n-propylamine, di-i-propylamine, di-n
-Butylamine, di-i-butylamine, di-sec-
Linear, branched or cyclic dialkylamines such as butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine and dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n
-Propylamine, tri-i-propylamine, tri-
n-butylamine, tri-i-butylamine, tri-s
ec-butylamine, tri-t-butylamine, tri-
linear, branched or cyclic trialkylamines such as n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;
Aminoethanol, 3-amino-1-propanol, 1
-Amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1
Linear, branched or cyclic monoalkanolamines such as -hexanol and 4-amino-1-cyclohexanol;

Diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, di-n-hexanolamine, di ( Linear, branched or cyclic dialkanolamines such as 4-cyclohexanol) amine; triethanolamine, tri-n-propanolamine, tri-i-
Linear, branched or cyclic such as propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4-cyclohexanol) amine Trialkanolamines;

3-amino-1,2-propanediol,
2-amino-1,3-propanediol, 4-amino-
1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3
Linear or linear such as -dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, and 2-diethylamino-1,3-propanediol; Branched amino group-containing alkane diols; 1-aminocyclopentanemethanol, 3-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-
Amino group-containing cycloalkane methanols such as aminocyclohexanemethanol, 3-dimethylaminocyclopentanemethanol, 3-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, and 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-
Aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1
And aminocarboxylic acids such as -aminocyclohexanecarboxylic acid and 4-aminocyclohexanecarboxylic acid.

Examples of the phenyl group-containing amine include a compound in which an amino group is directly bonded to a phenyl group and a compound in which an amino group is bonded to a phenyl group via a carbon chain. Examples of the phenyl group-containing amine include aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, and 4-n-butyl. Aniline, 4-t-butylaniline, 1-naphthylamine, 2-naphthylamine, N, N
-Dimethylaniline, N, N-diethylaniline, 4-
Aromatic amines such as methyl-N, N-dimethylaniline; containing amino groups such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, and 4-diethylaminobenzyl alcohol; Benzyl alcohols; 2-aminophenol, 3-aminophenol,
Examples thereof include amino group-containing phenols such as 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, monoalkanolamines are preferred as aliphatic amines from the viewpoint of solubility in a solvent described below, prevention of background fouling and film residue on the unexposed portion on the substrate or light-shielding layer, and the like. And amino group-containing alkanediols are preferred, especially 2-
Aminoethanol, 3-amino-1-propanol, 5
-Amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like are preferred. Further, as the phenyl group-containing amine, amino group-containing phenols are preferable, and 2-aminophenol, 3-aminophenol, 4-aminophenol and the like are particularly preferable. The organic amino compounds can be used alone or in combination of two or more.

The compounding amount of the organic amino compound is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition [I]. In this case, if the amount of the organic amino compound used exceeds 15% by weight, the adhesion of the formed spacer to the substrate tends to decrease.

Further, additives other than the organic acids and organic amino compounds include, for example, dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives; fillers such as glass and alumina; polyvinyl alcohol; Polyethylene glycol monoalkyl ethers,
Polymer compounds such as poly (fluoroalkyl acrylate); nonionic, cationic, anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane;
N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)
Adhesion promoters such as ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; 2,2′-thiobis ( 4-methyl-6-t-
Antioxidants such as butylphenol) and 2,6-di-t-butylphenol; and ultraviolet absorption such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones. Agents; anticoagulants such as sodium polyacrylate;
Thermal radical generators such as 1'-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile can be mentioned.

The solvent radiation-sensitive composition [I] contains the above-mentioned components (A) to (D) as essential components and optionally contains the above-mentioned additive components. It is prepared as a product. Examples of the solvent include those which disperse or dissolve the components (A) to (D) and the additives constituting the radiation-sensitive composition [I], do not react with these components, and have appropriate volatility. Can be appropriately selected and used. Specific examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-ethyl. n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n -Butyl ether, dipropylene glycol monomethyl acrylate Le, dipropylene glycol monoethyl ether, dipropylene glycol mono -
n-propyl ether, dipropylene glycol mono-
(poly) alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether;

(Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; methyl ethyl ketone;
Ketones such as cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate;
Alkyl lactates such as ethyl hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate;
Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, N-butyric acid
Other esters such as butyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methyl Amides such as pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be mentioned.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether,
Diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxy Butyl propionate, n-butyl acetate, i-butyl acetate,
Preferred are n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like. The solvents may be used alone or in combination of two or more.

Also, benzyl ethyl ether, di-n-hexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, High boiling solvents such as diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate can also be used in combination. These high-boiling solvents can be used alone or in combination of two or more.

The amount of the solvent to be used is not particularly limited, but from the viewpoint of the applicability, stability and the like of the radiation-sensitive composition [I] to be obtained, the amount of each component excluding the solvent of the composition is reduced. The total concentration is usually 5 to 50% by weight, preferably 10 to 50% by weight.
An amount of 40% by weight is desirable.

Method for Forming Color Filter Next, a substrate for driving a thin film transistor (TFT) type color liquid crystal display device (hereinafter, referred to as “TFT type driving substrate”) using the radiation-sensitive composition [I]. Above, a method of forming the spacer or the pixel and / or the black matrix will be described. When forming a pixel, usually, a coloring agent, an alkali-soluble resin,
A radiation-sensitive composition containing a polyfunctional monomer and a photopolymerization initiator is used. The colorant used for forming the pixel or the black matrix is not particularly limited in color tone, and may be any of pigments, dyes and natural pigments, but has high coloring properties and high heat decomposition resistance. Agent is desirable, and for the formation of pixels, preferably
One or more organic pigments are used as the colorant, and two or more organic pigments and / or carbon black are preferably used as the colorant for forming the black matrix.

Examples of the colorant used for forming the pixels or the black matrix include the same organic pigments and inorganic pigments containing carbon black as exemplified for the radiation-sensitive composition [I].
Examples of the alkali-soluble resin, the polyfunctional monomer, and the photopolymerization initiator used for forming the pixel or the black matrix include, for example, the alkali-soluble resin exemplified for the radiation-sensitive composition (I), and the polyfunctional monomer. The same thing as a monomer and a photoinitiator can be mentioned. The additives described for the radiation-sensitive composition [I] can be added to the radiation-sensitive composition used when forming the pixels or the black matrix. The radiation-sensitive resin composition used when forming the pixel or the black matrix is also usually prepared as a liquid composition by blending a solvent. As the solvent, for example, the same solvents as those exemplified for the radiation-sensitive composition [I] can be mentioned.

For the spacer, for example, using three radiation-sensitive compositions [I] of red, green and blue, the red, green and blue pixels are respectively formed in a single layer on the TFT type driving substrate, that is, A layer formed from the radiation-sensitive composition (I) of each color is formed so that the pixels of each color do not overlap and are arranged in a predetermined arrangement, and at locations other than the pixel portion and the black matrix portion. A method of laminating three layers and using this laminated portion as a spacer;

The black radiation-sensitive composition [I] can be formed by a method of forming a spacer pattern on a portion other than the pixel portion and the black matrix portion on the TFT-type driving substrate, or the like. In the methods (1) and (2), a black matrix can be further formed on the TFT-type driving substrate in some cases.
In another method, pixels and / or a black matrix can be further formed on a TFT-type driving substrate in some cases.

When the spacer is formed by the method described in the above, if necessary, the spacer is formed on the surface of the TFT type driving substrate.
Forming a light-shielding layer so as to partition a portion where a pixel is formed,
After applying, for example, a liquid composition of the radiation-sensitive composition [I] in which a red pigment is dispersed on the substrate, prebaking is performed to evaporate the solvent to form a coating film. Then
After exposing this coating film through a photomask for simultaneously forming pixels and spacers, developing using an alkaline developer to dissolve and remove unexposed portions of the coating film, and then post-baking. Accordingly, a pixel array in which red pixels of a predetermined shape are arranged in a predetermined arrangement and a red spacer pattern of a predetermined shape are formed on the TFT driving substrate.

Thereafter, using a liquid composition of each radiation-sensitive composition [I] in which a green or blue pigment is dispersed, coating, pre-baking, exposure, development and post-treatment of each liquid composition in the same manner as described above. Baking is performed, and each pixel array in which green pixels and blue pixels each having a predetermined shape are arranged in a single layer in a predetermined arrangement, and a spacer having a predetermined shape in which red, green or blue spacer patterns are laminated in three layers Are formed on the same TFT driving substrate to obtain a color filter. However, the order of forming the pixel arrays of each color when forming the color filters is not limited to the above.

When the spacer is formed by the method described above, a liquid composition of the radiation-sensitive composition [I] in which a black pigment is dispersed is applied onto a TFT driving substrate, and then prebaked. To evaporate the solvent to form a coating. Next, after the coating film is exposed through a photomask for forming a spacer, it is developed using an alkaline developer to dissolve and remove unexposed portions of the coating film,
Thereafter, post-baking is performed to form a black spacer pattern having a predetermined shape on the TFT driving substrate.

The liquid composition of the radiation-sensitive composition [I] was
When applying to the FT driving substrate, an appropriate coating method such as spin coating, casting coating, roll coating, or the like can be adopted. The coating thickness is usually 0.1
It is from 10 to 10 m, preferably from 0.2 to 8.0 m, particularly preferably from 0.2 to 6.0 m. As the radiation used when producing the color filter, for example, visible light, ultraviolet light, far ultraviolet light, an electron beam, X-rays and the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable. . The radiation exposure amount is preferably 10 to
It is 10,000 J / m ² .

Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-.
Undecene, 1,5-diazabicyclo- [4.3.0]
An aqueous solution such as -5-nonene is preferred. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkali developer. As a developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid puddle) developing method, or the like can be applied. The development conditions are preferably at room temperature for 5 to 300 seconds. After the alkali development, washing is usually performed with water. Further, the pixels and the black matrix further formed in some cases can be formed according to the above-described method.

The total deformation of the cured product formed from the radiation-sensitive composition [I] in the indentation hardness measurement at 25 ° C. is within 2 μm, preferably within 1.5 μm. The total deformation in the indentation hardness measurement is within 2.5 μm, preferably within 2.0 μm. Here, the indentation hardness at each temperature was as follows: a cured product having a thickness of 5 μm was cured at 25 ° C. or 180 ° C. using a 115 ° triangular pyramid indenter made of diamond at a load speed of 0.27 g.
f / sec, a value measured by pushing with a maximum load of 3 gf / cm ² , and the total deformation is the sum of the elastic deformation and the plastic deformation. Further, the elastic deformation ratio (= 100 × elastic deformation amount / total deformation amount) in the indentation hardness measurement at 25 ° C. of the cured product is preferably 20% or more, more preferably 30% or more.
% Or more, and the elastic deformation ratio (= 100 × elastic deformation amount / total deformation amount) in the indentation hardness measurement at 180 ° C. of the cured product is preferably 20% or more, and more preferably 30% or more.
% Or more.

[0086]

BEST MODE FOR CARRYING OUT THE INVENTION The radiation-sensitive composition [I] contains the above-mentioned components (A) to (D) as essential components. (A) to (f). (A) A radiation-sensitive composition [I] wherein (B) the alkali-soluble resin contains a carboxyl group-containing copolymer, more preferably a carboxyl group-containing copolymer (α). (B) (C) The polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate.
Radiation-sensitive composition [I]. (C) The radiation-sensitive composition of (A) or (B), wherein (A) the colorant contains a red or green colorant, and (D) the photopolymerization initiator contains an acetophenone-based compound and / or a triazine-based compound. Object [I]. (D) the colorant (A) contains a blue colorant; and (D) the photopolymerization initiator contains a biimidazole compound.
Or (b) the radiation-sensitive composition [I]. (E) The radiation-sensitive composition of (A) or (B), wherein (A) the colorant contains a black colorant, and (D) the photopolymerization initiator contains an acetophenone-based compound and / or a biimidazole-based compound. [I]. (F) The photopolymerization initiator containing a biimidazole-based compound (D), wherein the photopolymerization initiator further contains a hydrogen donor.
Radiation-sensitive composition [I].

Further, preferred spacers of the present invention are:
Or (f) a spacer for a thin film transistor (TFT) type color liquid crystal display device formed from the radiation-sensitive composition [I]. Further, a preferred color color liquid crystal display device of the present invention is (h) a thin film transistor (TFT) type color color liquid crystal display device having the spacer of (h).

[0088]

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Example 1 (A) CI Pigment Red 177 and CI
100 parts by weight of a 65/35 (weight ratio) mixture of C.I. / 15/35/10/2
5, Mw = 30,000, Mn = 10,000) 70 parts by weight, (C) 80 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 1- (4-) as a photopolymerization initiator. 50 parts by weight of morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to form a liquid of the radiation-sensitive composition [I]. Composition (R1) was prepared.

Next, the liquid composition (R1) was applied using a spin coater on the surface of a substrate in which a silicon nitride film was formed on the surface of a TFT type liquid crystal driving substrate.
Prebaking was performed for 10 minutes in a clean oven at 0 ° C. to form a coating film having a thickness of 6.6 μm. Thereafter, the substrate is cooled to room temperature, and the coating film is applied to a coating film of 365 nm, 405 nm using a high-pressure mercury lamp without using a photomask.
UV light containing each wavelength of 2,000 nm and 436 nm
Exposure was performed at an exposure amount of 0 J / m ² . Thereafter, a process for forming an actual spacer on this substrate, that is, 2
The film was immersed in a 0.1% by weight aqueous solution of tetramethylammonium hydroxide at 3 ° C. for 1 minute for development, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 25 minutes to form a red continuous cured film having a thickness of 5 μm on the substrate.

Evaluation of hardness: When the indentation hardness of the obtained continuous cured film was measured at 25 ° C., the total deformation was 1.82 μm and the elastic deformation ratio was 35%.
When the indentation hardness was measured at 180 ° C. for the same continuously cured film, the total deformation was 2.36 μm and the elastic deformation ratio was 26%.

Evaluation of Adhesion (1): The liquid composition (R1) was applied to a glass substrate on which a silicon dioxide film was formed using a spin coater, and then prebaked in a 90 ° C. clean oven. A coating film having a thickness of 6.6 μm was formed. Then, after this coating film was cooled to room temperature, 20 × 2
Using a high-pressure mercury lamp through a photomask for forming a dot pattern of 0 μm, ultraviolet rays having wavelengths of 365 nm, 405 nm and 436 nm were irradiated at 2,000 J /
Exposure was performed at an exposure dose of m ² . Thereafter, the coating film was shower-developed with a 0.05% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds (23 ° C., development pressure: 1.
5 kgf / cm ² ) and then use ultrapure water for 60
After washing for 23 seconds (23 ° C., washing pressure: 2.0 kgf / cm ² ), a 20 × 20 μm dot pattern was formed. After that, when the dot pattern formed on the substrate was observed with a microscope, no lack of the pattern was observed at all, and the adhesion was excellent.

Evaluation of adhesion (2): The liquid composition (R1) was applied to a glass substrate on which a silicon dioxide film was formed using a spin coater, and then prebaked in a clean oven at 90 ° C. A coating film having a thickness of 6.6 μm was formed. Thereafter, the coating film was cooled to room temperature, and then passed through a high-pressure mercury lamp without using a photomask.
Ultraviolet rays having respective wavelengths of nm, 405 nm and 436 nm were exposed at an exposure amount of 2,000 J / m ² . afterwards,
The coating film was shower-developed with a 0.05% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds (2
3 ° C., developing pressure: 1.5 kgf / cm ² )
Washing using ultrapure water for 60 seconds (23 ° C., washing pressure: 2.0
Kgf / cm ² ). Thereafter, post-baking was performed in a 220 ° C. clean oven for 25 minutes to form a red continuously cured film on the substrate. Next, the obtained continuous cured film was cut with a cutter in 10 vertical rows and 10 horizontal rows at 1 mm intervals.
Make a cut in the grid pattern of the line and follow JIS K5400
A tape peeling test was performed according to 8.5. As a result, no chipping or peeling occurred in the grid.

Example 2 (A) CI Pigment Red 177 and CI
100 parts by weight of a 65/35 (weight ratio) mixture of C.I. / 15/35/10/2
5, Mw = 30,000, Mn = 10,000) 70 parts by weight, (C) 80 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 1- [4- as a photopolymerization initiator. (Methylthio) phenyl] -2-methyl-2-morpholinopropan-1-one 20 parts by weight, 4,4'-bis (diethylamino) benzophenone 15 parts by weight as a sensitizer, and propylene glycol monomethyl ether acetate 1 as a solvent 2,000 parts by weight of a liquid-sensitive composition (R2)
Was prepared. Next, a 5 μm-thick red continuous cured film was formed on the substrate in the same manner as in Example 1 except that the liquid composition (R2) was used instead of the liquid composition (R1).

Evaluation of hardness: When the indentation hardness of the obtained continuously cured film was measured at 25 ° C., the total deformation was 1.79 μm and the elastic deformation ratio was 36%.
When the indentation hardness was measured at 180 ° C. for the same continuously cured film, the total deformation was 2.21 μm and the elastic deformation ratio was 27%. Evaluation of adhesion (1): A 20 × 20 μm dot pattern was prepared in the same manner as in the evaluation of adhesion (1) in Example 1 except that the liquid composition (R2) was used instead of the liquid composition (R1). Was formed and observed with a microscope. As a result, no loss of the pattern was observed, and the adhesiveness was excellent. Evaluation of adhesion (2): A tape peeling test was performed in the same manner as in the evaluation of adhesion (2) in Example 1, except that the liquid composition (R2) was used instead of the liquid composition (R1). Was.
As a result, no chipping or peeling occurred in the grid.

Example 3 (A) CI Pigment Blue 15: 6 as a colorant and C.I.
I. 95/5 with Pigment Violet 23 (weight ratio)
55 parts by weight of a mixture, (B) a methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymer weight ratio = 15 /
15/70, Mw = 25,000, Mn = 10000
0) 75 parts by weight, (C) 75 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D)
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ as a photopolymerization initiator
-6 parts by weight of biimidazole, 6 parts by weight of 4,4'-bis (diethylamino) benzopheno as an amine hydrogen donor, 3 parts by weight of 2-mercaptobenzothiazole as a hydrogen donor of mercaptan, and propylene glycol monomethyl ether acetate as a solvent 700 parts by weight of cyclohexanone and 300 parts by weight of cyclohexanone were mixed to prepare a liquid composition (B1) of the radiation-sensitive composition. Next, a film having a thickness of 5 μm was formed on the substrate in the same manner as in Example 1 except that the liquid composition (B1) was used instead of the liquid composition (R1).
m, a blue continuous cured film was formed.

Evaluation of hardness: The obtained continuously cured film was subjected to indentation hardness measurement at 25 ° C., and as a result, the total deformation was 1.61 μm and the elastic deformation ratio was 39%.
When the indentation hardness was measured at 180 ° C. for the same continuously cured film, the total deformation was 2.09 μm and the elastic deformation ratio was 27%. Evaluation of Adhesion (1): A 20 × 20 μm dot was prepared in the same manner as in Evaluation of Adhesion (1) of Example 1, except that the liquid composition (B1) was used instead of the liquid composition (R1). When the pattern was formed and observed with a microscope, no lack of the pattern was observed at all, and the adhesion was excellent. Evaluation of adhesion (2): A tape peeling test was performed in the same manner as in the evaluation of adhesion (2) in Example 1, except that the liquid composition (B1) was used instead of the liquid composition (R1). Was.
As a result, no chipping or peeling occurred in the grid.

Example 4 (A) CI Pigment Green 36 and CI
100 parts by weight of a 65/35 (weight ratio) mixture with CI Pigment Yellow 150, and (B) a methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymer weight ratio = 15 /
15/70, Mw = 25,000, Mn = 10000
0) 75 parts by weight, (C) 75 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D)
10 parts by weight of a triazine compound (3) as a photopolymerization initiator, 700 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and cyclohexanone 3
The liquid composition (G1) of the radiation-sensitive composition was prepared by mixing 00 parts by weight. Next, a 5 μm-thick green continuous cured film was formed on the substrate in the same manner as in Example 1 except that the liquid composition (G1) was used instead of the liquid composition (R1).

Evaluation of Hardness: The indentation hardness of the obtained continuously cured film was measured at 25 ° C., and the result was a total deformation of 1.57 μm and an elastic deformation ratio of 39%.
When the indentation hardness was measured at 180 ° C. for the same continuous cured film, the total deformation was 2.03 μm and the elastic deformation ratio was 40%. Evaluation of adhesion (1): A 20 × 20 μm dot was prepared in the same manner as in the evaluation of adhesion (1) in Example 1 except that the liquid composition (G1) was used instead of the liquid composition (R1). When the pattern was formed and observed with a microscope, no lack of the pattern was observed at all, and the adhesion was excellent. Evaluation of adhesion (2): A tape peeling test was performed in the same manner as in the evaluation of adhesion (2) in Example 1 except that the liquid composition (G1) was used instead of the liquid composition (R1). Was.
As a result, no chipping or peeling occurred in the grid.

Example 5 Using the liquid composition (G1) prepared in Example 4, a coating film having a thickness of 2.2 μm was formed in the same manner as in Example 1. Then, after cooling the substrate to room temperature, a high-pressure mercury lamp was used through a photomask for simultaneously forming pixels and spacers, and the coating film was irradiated with ultraviolet light having wavelengths of 365 nm, 405 nm, and 436 nm for 2 hours. 000J /
Exposure was performed at an exposure dose of m ² . Thereafter, the substrate was immersed in a 0.1% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 1 minute for development, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed in a 220 ° C. clean oven for 25 minutes to form a pixel array in which green pixels of a predetermined shape were arranged and a green spacer pattern on the substrate.

Next, a 2.2 μm-thick coating film was formed on the obtained substrate in the same manner as in Example 1 using the liquid composition (B1) prepared in Example 3, and Similarly, a pixel array in which a blue pixel pattern of a predetermined shape was arranged in a single layer was formed on a substrate, and a blue spacer pattern was laminated on a green spacer pattern. Next, using the liquid composition (R1) prepared in Example 1 on the obtained substrate, in the same manner as in Example 1,
After forming a coating film having a thickness of 2.2 μm, a pixel array in which green pixels, blue pixels and red pixels of a predetermined shape are respectively arranged in a single layer on the substrate is formed in the same manner as described above. The red spacer pattern was laminated on the blue spacer pattern, and the three-layer spacer pattern was laminated in the order of green, blue and red,
A 5 μm-thick spacer having a predetermined shape was formed.

Evaluation of display panel: When a display panel was assembled using the obtained substrate and evaluated, no deformation or destruction of the spacer was observed, and no display defects such as display unevenness occurred.

Example 6 (A) CI Pigment Blue 15: 6 as a colorant and C.I.
I. Pigment Yellow 150 and CI Pigment Red 1
250 parts by weight of a 15/15/60/10 (weight ratio) mixture of 77 and barium sulfate; (B) methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymer weight ratio =
15/15/70, Mw = 25,000, Mn = 10,
000) 80 parts by weight, (C) 70 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer,
(D) 1- (4-morpholinophenyl) -2-benzyl-2-dimethylaminobutane-1 as a photopolymerization initiator
-One 60 parts by weight and 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'
-12 parts by weight of biimidazole and 4,4'-bis (diethylamino) benzopheno 12 as an amine hydrogen donor
Parts by weight, 6 parts by weight of 2-mercaptobenzothiazole as a mercaptan-based hydrogen donor, and 500 parts by weight of propylene glycol monomethyl ether acetate and 500 parts by weight of cyclohexanone as solvents are mixed to form a liquid composition of a radiation-sensitive composition (BL1 ) Was prepared. Except that the liquid composition (BL1) was used instead of the liquid composition (R1) and the exposure amount was set to 5,000 J / m ² , a 5 μm-thick black A continuous cured film was formed.

Evaluation of hardness: When the indentation hardness of the obtained continuous cured film was measured at 25 ° C., the total deformation was 1.51 μm and the elastic deformation ratio was 33%.
When the indentation hardness was measured at 180 ° C. for the same continuous cured film, the total deformation was 2.01 μm and the elastic deformation ratio was 28%. Evaluation of Adhesion (1): A liquid composition (BL1) was used instead of the liquid composition (R1), and the exposure amount was 5,000 J / m.
Except for using ^2, in the same manner as in the evaluation of adhesion of Example 1 (1), by forming a dot pattern of 20 × 20 [mu] m,
Observation with a microscope revealed that no lack of pattern was observed and the adhesion was excellent.

Evaluation of adhesion (2): Liquid composition (R1)
Was used instead of the liquid composition (BL1), and the exposure amount was 5,
A tape peeling test was carried out in the same manner as in the evaluation of adhesion (2) in Example 1 except that 000 J / m ² was used. As a result, no chipping or peeling occurred in the grid. Evaluation of display panel: 5,0 using a liquid composition (BL1) through a photomask for forming a spacer.
A columnar spacer pattern was formed on a substrate in the same manner as in Example 1 except that exposure was performed at an exposure amount of 00 J / m ² . When a display panel was assembled using the obtained substrate and evaluated, no deformation or destruction of the spacer was observed, and no display defect such as display unevenness occurred.

[0105]

According to the radiation-sensitive composition [I] of the present invention, the cured product has a sufficient strength and excellent adhesion to a substrate. Since no destruction occurs and no display defects such as display unevenness occur, a high quality and highly reliable color liquid crystal display device can be manufactured with high productivity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 5/20 101 G02B 5/20 101 4J026 G02F 1/1339 500 G02F 1/1339 500 1/1368 1/1368 G03F 7/027 502 G03F 7/027 502 7/029 7/029 (72) Inventor Osamu Abe 2-11-11 Tsukiji 2-chome, Chuo-ku, Tokyo FSR term in JSR Corporation (reference) 2H025 AA02 AA04 AB13 AB14 AC01 AD01 BC13 BC82 BJ07 CA02 CA14 CA28 CB13 CB43 CC11 2H048 BA02 BA45 BA48 BB02 BB08 BB12 BB42 2H089 LA01 QA12 TA09 TA12 TA13 TA18 2H092 JA24 JB57 KB24 MA05 NA29 PA03 PA08 PA09 PA13 4J011 PA69 PA01 SA01 RA01 QA12 AA53 AC35 BA28 DB06 DB36 FA05 GA06

Claims (10)

[Claims] 1. A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator, obtained therefrom. A feeling used for forming a spacer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, wherein a total deformation amount of the cured product in the indentation hardness measurement at 25 ° C. is within 2 μm. Radioactive composition. 2. A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator, which is obtained therefrom. The cured product is used for forming a spacer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, characterized in that a total deformation amount in indentation hardness measurement at 180 ° C. is within 2.5 μm. Radiation-sensitive composition. 3. The method according to claim 1, wherein (B) the alkali-soluble resin comprises a copolymer of an ethylenically unsaturated monomer having at least one carboxyl group and another copolymerizable ethylenically unsaturated monomer. The radiation-sensitive composition according to claim 1 or 2. 4. The method according to claim 1, wherein the polyfunctional monomer (C) is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. 3. The radiation-sensitive composition according to item 1. 5. The method according to claim 1, wherein (A) the colorant includes a red or green colorant, and (D) the photopolymerization initiator includes an acetophenone-based compound and / or a triazine-based compound.
5. The radiation-sensitive composition according to any one of 4. 6. The colorant (A) includes a blue colorant,
(D) the photopolymerization initiator contains a biimidazole compound,
The radiation-sensitive composition according to claim 1. 7. The colorant (A) includes a black colorant,
(D) the photopolymerization initiator is an acetophenone-based compound and / or
The radiation-sensitive composition according to any one of claims 1 to 4, further comprising a biimidazole-based compound. 8. The radiation-sensitive composition according to claim 6, wherein (D) the photopolymerization initiator containing a biimidazole compound further contains a hydrogen donor. 9. A spacer for a thin film transistor (TFT) type color liquid crystal display device formed of the radiation-sensitive composition according to claim 1. Description: 10. A thin film transistor (TFT) type color liquid crystal display device comprising the spacer according to claim 9.