JP2001215324A - Radiation-sensitive composition for color liquid crystal display device and color liquid crystal display device - Google Patents

Abstract

(57) [Problem] To provide a conductive path such as a through hole or a U-shaped dent of 5 μm or less, no development residue at the time of development, and close contact with a driving substrate or a passivation film. Disclosed is a radiation-sensitive composition for a color liquid crystal display device, which has excellent properties and is used for forming a colored layer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. SOLUTION: The radiation-sensitive composition for a color liquid crystal display device comprises (A) a colorant, (B) an alkali-soluble resin, and (C)
A radiation-sensitive composition containing a polyfunctional monomer and (D) a photopolymerization initiator, wherein a conductive path of 5 μm or less can be formed in the colored layer, or the component (C) is It contains a carboxyl group-containing polyfunctional monomer, or further contains (E) a carboxyl group-containing monofunctional monomer in addition to the components (A) to (D).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color liquid crystal display device having a color layer containing pixels and / or a black matrix formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. The present invention relates to a radiation-sensitive composition for a liquid crystal display device and a color liquid crystal display device.

[0002]

2. Description of the Related Art In a color liquid crystal display device using a thin film transistor (TFT) substrate, conventionally, a color filter substrate for displaying a color image is manufactured separately from a driving substrate on which a thin film transistor (TFT) is arranged. Then, the color filter substrate is manufactured by bonding the color filter substrate to 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 that transmits light). There was a disadvantage that it was. On the other hand, in order to increase the aperture ratio of the liquid crystal panel, a thin film transistor (TF
A colored layer is formed directly or via a passivation film such as a silicon nitride film on the surface of the driving substrate on which T) is disposed, and the substrate on which the colored layer is formed is ITO (tin-doped) by sputtering. A method has been developed in which the substrate is bonded to a substrate on which an indium oxide (indium oxide) electrode is 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. By the way, the length of one side of the colored layer formed by the latter method is about 1 to 15 μm in order to conduct the ITO electrode disposed on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conductive path such as a rectangular through hole or a U-shaped depression, but in recent years, the size of the conductive path (that is, the length of one side) is particularly 5 μm.
m is required. However, a radiation-sensitive composition used to form a colored layer on a driving substrate of a conventional thin film transistor (TFT) type color liquid crystal display device could not form a conduction path of 5 μm or less.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a problem of 5 μm.
m, a conductive path such as a through hole or a U-shaped dent can be formed, and no development residue occurs during development, and a driving substrate or a silicon nitride film on which a thin film transistor (TFT) is disposed. Thin film transistor (TFT) with excellent adhesion to the passivation film
An object of the present invention is to provide a radiation-sensitive composition for a color liquid crystal display device used for forming a colored layer on a driving substrate of a color liquid crystal display device.

[0004]

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) an optically functional monomer. A driving substrate for a thin film transistor (TFT) type color liquid crystal display device, which is a radiation-sensitive composition containing a polymerization initiator and is capable of forming a conductive path of 5 μm or less with respect to the coloring layer when forming the coloring layer. This is achieved by a radiation-sensitive composition for a color liquid crystal display device used for forming a colored layer thereon.

According to the present invention, the above-mentioned problem is secondly achieved.
A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, wherein (C) a polyfunctional monomer. A color used for forming a colored layer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, wherein a part or the whole of the body is made of a carboxyl group-containing polyfunctional monomer. This is achieved by a radiation-sensitive composition for a liquid crystal display device.

[0006] According to the present invention, the above-mentioned problem is, thirdly,
(A) a coloring agent, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photopolymerization initiator, and (E) a carboxyl group-containing monofunctional monomer. This is achieved by a radiation-sensitive composition for a color liquid crystal display device used for forming a colored layer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. The term “radiation” as used in the present invention means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray 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 is appropriately selected depending on the use of the obtained color filter, and may be any of a pigment, a dye, and a natural pigment.
Since the color filter is required to have high definition color development and heat resistance, as the colorant in the present invention, a colorant having a high color development property, and a colorant having high heat resistance, particularly a colorant having high heat decomposition resistance is preferable, and is usually , Pigments, particularly preferably organic pigments and / or carbon black.

Examples of the organic pigment include a color index (CI; The Society of Dyers and Coloris).
Compounds classified as Pigment (published by ts Co., Ltd.), specifically those having a color index (CI) number as shown below. CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16,
CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI
Pigment Yellow 65, CI Pigment Yellow 7
1, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97,
CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, C.I.
I. Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, C.I.
I. Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, C.I.
CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, C.I.
Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, C.I.
I. Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175, C.I.
I. Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 190;

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, C.I.
I. Pigment Orange 17, CI Pigment Orange 2
4, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49,
CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Violet 1, C.I.
I. Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38;

[0010] CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 1
0, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI
Pigment Red 41, CI Pigment Red 42, C.I.
I. Pigment Red 48: 1, CI Pigment Red 4
8: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, C.I.
I. Pigment Red 49: 2, CI Pigment Red 5
0: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57:
2, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63:
2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI
Pigment Red 97, CI Pigment Red 101,
CI Pigment Red 102, CI Pigment Red 1
04, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI
Pigment Red 114, CI Pigment Red 12
2, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166,
CI Pigment Red 168, CI Pigment Red 1
70, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI
Pigment Red 177, CI Pigment Red 17
8, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193,
CI Pigment Red 194, CI Pigment Red 2
02, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI
Pigment Red 216, CI Pigment Red 22
0, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255,
CI Pigment Red 264, CI Pigment Red 2
65;

CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, C.I.
I. Pigment Blue 15: 6, CI Pigment Blue 6
0; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25; 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 inorganic pigments 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. When the radiation-sensitive composition for a color liquid crystal display device of the present invention is used for forming a pixel, preferably, one or more organic pigments are used as a coloring agent, and in order to form a black matrix. If used, preferably two or more organic pigments and / or carbon black are used as colorants.

In the present invention, each of the above pigments can be used after modifying the particle surface thereof with a polymer, if desired. Examples of the polymer for modifying the particle surface of the pigment include a polymer described in JP-A-8-259876 and various commercially available polymers or oligomers for dispersing pigments. The colorant in the present invention can be used together with a dispersant, if desired. Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octyl phenyl ether and polyoxyethylene n-nonyl phenyl ether; polyethylene glycol dilaurate and polyethylene glycol distearate Polyethylene glycol diesters; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; polyethylene imines, etc .; Chemical Co., Ltd.), F Top (Tochem Products), Megafac (Dainippon Ink and Chemicals), Florard (Sumitomo 3M),
Asahi Guard, Surflon (all made by Asahi Glass Co., Ltd.),
Disperbyk (Big Chemie Japan Co., Ltd.)
), Solsperse (manufactured by Zeneca Corporation), EFKA (manufactured by EFKA Chemicals Corporation), and the like. These surfactants can be used alone or in combination of two or more. The amount of the surfactant to be used is generally 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the coloring agent.

(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 treatment step when a color filter is produced; Particularly preferably, it is not particularly limited as long as it has solubility in an alkali developing solution.
A copolymer of a polymerizable unsaturated monomer having an acidic functional group such as sulfonic acid and another copolymerizable unsaturated monomer (hereinafter, referred to as “copolymerizable unsaturated monomer”). Can be mentioned.

The polymerizable unsaturated monomer having a carboxyl group (hereinafter referred to as “carboxyl group-containing unsaturated monomer”) includes, for example, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, Unsaturated monocarboxylic acids such as cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; and anhydrides thereof; Or more unsaturated polycarboxylic acids or anhydrides thereof; di- or more-valent such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate; Mono [(meth) acryloyloxyalkyl] esters of polycarboxylic acids;
Examples thereof include polymer mono (meth) acrylates having a carboxyl group and a hydroxyl group at both ends such as ω-carboxypolycaprolactone mono (meth) acrylate. Among these carboxyl group-containing unsaturated monomers, (meth) acrylic acid, succinic acid mono [2-
(Meth) acryloyloxyethyl] and the like.

The polymerizable unsaturated monomer having a phenolic hydroxyl group includes, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy- α-methylstyrene, p-hydroxy-α-methylstyrene, No-hydroxyphenylmaleimide,
Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide and the like can be mentioned. Examples of the polymerizable unsaturated monomer having a sulfonic acid group include isoprenesulfonic acid and p-styrenesulfonic acid. The polymerizable unsaturated monomers having an acidic functional group can be used alone or in combination of two or more.

Next, examples of the copolymerizable unsaturated monomer include, for example, a mono () at the terminal of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane. Macromonomers having a (meth) acryloyl group (hereinafter, simply referred to as “macromonomers”): N-phenylmaleimide, N
-O-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, N-
m-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide,
N- (substituted) arylmaleimides such as Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide, and N-substituted maleimides such as N-cyclohexylmaleimide;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-
Methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Aromatic vinyl compounds; indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (Meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-
Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2 Phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) Acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, the following formula (3)

[0020]

Embedded image [In the formula (3), R ¹ represents a hydrogen atom or a methyl group. ]

Unsaturated carboxylic esters such as a monomer represented by the following formula (hereinafter referred to as "glycerol (meth) acrylate"); 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate ,
Unsaturated carboxylic acid aminoalkyl esters such as 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 3-dimethylaminopropyl (meth) acrylate; glycidyl ( Unsaturated carboxylic acid glycidyl esters such as meth) acrylate; vinyl carboxylic acid 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 Class; (meth) acrylonitrile, α
-Vinyl cyanide compounds such as chloroacrylonitrile and vinylidene cyanide; unsaturated amides such as (meth) acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; 1,3-butadiene, isoprene and chloroprene And other aliphatic conjugated dienes.

Among these copolymerizable unsaturated monomers, macromonomers, N-substituted maleimides, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, and glycerol (meth) acrylate are preferred. Among macromonomers, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer are particularly preferable, and among N-substituted maleimides, N-phenylmaleimide and N-cyclohexylmaleimide are particularly preferable. The copolymerizable unsaturated monomers can be used alone or in combination of two or more.

As a preferable alkali-soluble resin in the present invention, a copolymer of a carboxyl group-containing unsaturated monomer and a copolymerizable unsaturated monomer (hereinafter, simply referred to as "carboxyl group-containing copolymer"). Can be mentioned.
Examples of the carboxyl group-containing copolymer include a carboxyl group-containing unsaturated monomer, a polystyrene macromonomer, a polymethyl (meth) acrylate macromonomer,
N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth)
A monomer containing at least one selected from the group of acrylates, and optionally further containing at least one selected from the group of styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate A copolymer of a mixture (hereinafter, referred to as “carboxyl group-containing copolymer (I)”) is preferable,
In particular, a carboxyl group-containing unsaturated monomer component containing (meth) acrylic acid as an essential component and optionally further containing mono [2- (meth) acryloyloxyethyl] succinate; a polystyrene macromonomer; ) At least one selected from the group consisting of acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate, A copolymer of a monomer mixture further containing at least one selected from the group consisting of styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate (hereinafter, referred to as “carboxyl group-containing copolymer ( II) ") is good Arbitrariness.

Specific examples of the carboxyl group-containing copolymer (II) include (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate /
Polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / monosuccinic acid [2- (meth) acryloy Roxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer, (meth) acrylic acid / monosuccinic acid [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / benzyl (meth)
Acrylate / styrene copolymer, (meth) acrylic acid / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid /
Monosuccinate [2- (meth) acryloyloxyethyl]
/ N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer, (meth) acrylic acid /
Monosuccinate [2- (meth) acryloyloxyethyl]
/ N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monosuccinic acid [2- (meth) acryloyloxyethyl] / benzyl (meth) Acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / 2-
Hydroxyethyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / Phenyl (meth) acrylate copolymer (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) Acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid /
Examples thereof include N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer.

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, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the obtained radiation-sensitive composition in an alkali developing solution tends to decrease, while if it exceeds 50% by weight. In addition, the solubility in an alkali developing solution becomes excessive, and when developing with an alkali developing solution, there is a tendency that pixels are likely to fall off from the substrate or to become rough on the pixel surface.

The alkali-soluble resin used in the present invention preferably has a weight average molecular weight in terms of polystyrene (hereinafter, referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of 3,000 to 300, 000, and more preferably 5,000 to 100,000. In addition, the number average molecular weight in terms of polystyrene (hereinafter, referred to as “polycarbonate”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention.
It is called “Mn”. ) Is preferably from 3,000 to 60,
000, more preferably 5,000 to 25,000. By using such an alkali-soluble resin having a specific Mw or Mn, a radiation-sensitive composition excellent in developability can be obtained, whereby a pixel having a sharp pattern edge can be formed, During development, residues, background stains, film residues, and the like hardly occur on the unexposed portion of the substrate and the light-shielding layer. Further, the ratio of Mw and Mn of the alkali-soluble resin in the present invention (Mw /
Mn) is usually 1 to 5, preferably 1 to 4. In the present invention, the alkali-soluble resin may be used alone or
A mixture of more than one species can be used.

The amount of the alkali-soluble resin used in the present invention is usually 10 parts by weight per 100 parts by weight of the colorant (A).
１，1,000 parts by weight, preferably 20-500 parts by weight. In this case, when the use amount of the alkali-soluble resin is less than 10 parts by weight, for example, alkali developability is reduced,
There is a risk that background contamination or film residue may occur on the unexposed portion of the substrate or on the light-shielding layer. On the other hand, if it exceeds 1,000 parts by weight, the concentration of the colorant relatively decreases, so It may be difficult to achieve the concentration.

(C) Polyfunctional Monomer The polyfunctional monomer in the present invention comprises a monomer having two or more polymerizable unsaturated bonds. Multifunctional monomers are
It can be classified into a carboxyl group-containing polyfunctional monomer and a polyfunctional monomer having no carboxyl group (hereinafter, referred to as "other polyfunctional monomers"). Examples of the carboxyl group-containing polyfunctional monomer include, for example, a free carboxyl group-containing polyfunctional ester of a dihydric or higher polyhydric alcohol and a polymerizable unsaturated carboxylic acid having two or more carboxyl groups. Free carboxyl group-containing esterified product of a free hydroxyl group-containing polyfunctional ester of a trihydric or higher polyhydric alcohol with a polymerizable unsaturated carboxylic acid having one or more carboxyl groups and a dicarboxylic acid (hereinafter, referred to as ""(C1) Multifunctional monomer"); 3
Free carboxyl group-containing polyfunctional esterified product of a polyvalent carboxylic acid having a valency of at least one and a polymerizable unsaturated compound having at least one hydroxyl group (hereinafter referred to as “(C2) polyfunctional monomer”)
That. ) And the like.

The carboxyl group-containing polyfunctional monomer in the present invention includes (C1) a polyfunctional monomer and (C2)
Polyfunctional monomers are preferred. (C1) In the polyfunctional monomer, as a trihydric or higher polyhydric alcohol, for example,
Examples include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like. Examples of the polymerizable unsaturated carboxylic acid having one or more carboxyl groups include (meth) acrylic acid, crotonic acid, and α-chloro. Acrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like, and examples of the dicarboxylic acids include, for example, 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, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3 -Dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid Phthalic acid, isophthalic acid, and terephthalic acid.

In the (C2) polyfunctional monomer,
Examples of the trivalent or higher polycarboxylic acids include, for example, propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, aconitic acid, camphoronic acid, cyclohexane-1, 2,3-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid, melophanic acid, Examples thereof include pyromellitic acid. Examples of the polymerizable unsaturated compound having one or more hydroxyl groups include (meth) allyl alcohol, 2-hydroxyethyl (meth) acrylate,
Examples thereof include 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate.

Specific examples of the preferred (C1) polyfunctional monomer and (C2) polyfunctional monomer in the present invention will be described in more detail. Trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) ) Free carboxyl group-containing monoesters of monohydroxy group-containing oligo (meth) acrylates such as acrylate and dipentaerythritol penta (meth) acrylate with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid Propane-1,2,3-tricarboxylic acid, butane-1,2,4-tricarboxylic acid, benzene-
Tricarboxylic acids such as 1,2,3-tricarboxylic acid, trimellitic acid and trimesic acid, and monohydroxyalkyl (meth) such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate
Free carboxyl group-containing oligoesters with acrylates can be exemplified.

Among these (C1) polyfunctional monomer and (C2) polyfunctional monomer, particularly, free carboxyl of pentaerythritol triacrylate and succinic acid represented by the following formula (1): Group-containing monoester (hereinafter, referred to as “polyfunctional acrylate (1)”);
A free carboxyl group-containing monoester of pentaerythritol trimethacrylate and succinic acid represented by the following formula (2) (hereinafter, referred to as “polyfunctional methacrylate (2)”) is preferable.

[0034]

Embedded image

[0035]

Embedded image

Each of the polyfunctional acrylate (1) and the polyfunctional methacrylate (2) has a high pixel intensity,
It is possible to provide a radiation-sensitive composition having excellent smoothness on the surface of a pixel and hardly causing background dirt or film residue in a region other than a portion where a pixel is formed. In the present invention, the carboxyl group-containing polyfunctional monomer also has an effect of further improving the solubility characteristics of the radiation-sensitive composition in an alkali developer, and further suppressing the remaining undissolved material after development. And falls under the category of an organic acid component as an additive described later.

The other polyfunctional monomers include, for example, di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; and di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol. ) Acrylates;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol; oligo (meta) such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, and spirane resin ) Acrylates; hydroxypoly-1,3-butadiene at both ends;
Examples thereof include di (meth) acrylates of hydroxyl-terminated polymers such as hydroxy-polyisoprene at both ends and hydroxy-polycaprolactone at both ends, and tris [2- (meth) acryloyloxyethyl] phosphate.

Of these other polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols are preferred. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable, and particularly, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol Hexaacrylate is preferred because it has a high pixel strength, has excellent pixel surface smoothness, and is unlikely to cause background stain, film residue, and the like on the unexposed portion of the substrate and the light-shielding layer.

In the present invention, the polyfunctional monomers may be used alone or as a mixture of two or more kinds. The polyfunctional monomer having a carboxyl group and another polyfunctional monomer may be used. Can be used in combination, but it is preferable that a part or all of the polyfunctional monomer is a carboxyl group-containing polyfunctional monomer, whereby the radiation-sensitive composition for a color liquid crystal display device can be used. In forming the colored layer, a conductive path of 5 μm or less can be formed in the colored layer. In the present invention, the ratio of the carboxyl group-containing polyfunctional monomer to the total polyfunctional monomer when used is preferably 5 to 95% by weight, more preferably 10 to 80% by weight, and particularly preferably. 10 to 50% by weight. In this case, the use ratio of the carboxyl group-containing polyfunctional monomer is 5%.
If the amount is less than 10% by weight, it is difficult to form a required conducting path depending on the composition of the radiation-sensitive composition (particularly, when the (E) carboxyl group-containing monofunctional monomer described later is not used). On the other hand, when the content exceeds 95% by weight, the alkali developing solution easily penetrates into the colored layer, and the colored layer may be lost during development.

In the present invention, the amount of the polyfunctional monomer used is based on 100 parts by weight of the alkali-soluble resin (B).
Usually, it is 5 to 500 parts by weight, preferably 20 to 300 parts by weight, more preferably 50 to 150 parts by weight. In this case, if the amount of the polyfunctional monomer (c) used is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to decrease, while if it exceeds 500 parts by weight, for example, the alkali developability becomes poor. There is a tendency that the surface of the substrate or the light-shielding layer on the unexposed portion is liable to be stained, film residue, or the like.

(D) Photopolymerization Initiator The photopolymerization initiator in the present invention is radiation-sensitive by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray (hereinafter referred to as “exposure”). It is composed of a compound capable of generating an active species capable of initiating polymerization of each monomer constituting the acidic composition. As such a photopolymerization initiator,
For example, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, benzoin-based compounds, benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, xanthone-based compounds, diazo-based compounds, and the like can be given. In the present invention, the photopolymerization initiator can be used alone or as a mixture of two or more, and as the photopolymerization initiator in the present invention, an acetophenone-based compound, a biimidazole-based compound and a triazine-based compound are used. At least one selected from the group is preferred.

In the present invention, the photopolymerization initiator is generally used in an amount of usually 0.01 to 80 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of all monomers in the radiation-sensitive composition.
60 parts by weight. In this case, when the use amount of the photopolymerization initiator is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a colored layer array in which the colored layer patterns are arranged according to a predetermined arrangement. On the other hand, if it exceeds 80 parts by weight, the resolution of the conduction path tends to decrease.

Among the preferred photopolymerization initiators in the present invention, specific examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- ( Methylthio) phenyl]
-2-morpholinopropanone-1, 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)
Butanone-1, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the like. Among these acetophenone compounds, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4
-Morpholinophenyl) butanone-1 is preferred. The acetophenone-based compounds can be used alone or in combination of two or more.

In the present invention, when an acetophenone-based compound is used as a photopolymerization initiator, the amount used is usually based on 100 parts by weight of all monomers in the radiation-sensitive composition.
It is 0.01 to 80 parts by weight, preferably 1 to 60 parts by weight, more preferably 10 to 60 parts by weight. In this case, if the amount of the acetophenone-based compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a colored layer array in which the colored layer patterns are arranged according to a predetermined arrangement. On the other hand, if it exceeds 80 parts by weight, the resolution of the conduction path tends to decrease.

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.

Among these biimidazole compounds, 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'-tetra Phenyl-
1,2'-biimidazole and the like are preferred. These biimidazole-based compounds have excellent solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and allow the curing reaction to proceed sufficiently by exposure to a small amount of energy, and have high contrast. The exposed coating film is clearly divided into a cured part that is insoluble in the developer and an uncured part that has a high solubility in the developer because the curing reaction does not occur in the unexposed part. Is divided into
Thus, a high-definition pixel array in which pixel patterns without undercuts are arranged according to a predetermined arrangement can be formed. The biimidazole compounds can be used alone or in combination of two or more.

In the present invention, when a biimidazole compound is used as the photopolymerization initiator, the amount used is usually based on 100 parts by weight of all monomers in the radiation-sensitive composition.
It is 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the amount of the biimidazole-based compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a colored layer array in which the colored layer patterns are arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the resolution of the conduction path tends to decrease.

-Hydrogen Donor- In the present invention, when a biimidazole-based compound is used as the photopolymerization initiator, it is preferable to use a hydrogen donor described below in combination in that the sensitivity can be further 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 in the present invention, 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 has a benzene ring or a heterocyclic ring as a mother nucleus, and has one or more, preferably 1 to 3, amino groups directly bonded to the mother nucleus;
More preferably, it is composed of a compound having 1 to 2 compounds (hereinafter, referred to as “amine-based hydrogen donor”). Note that these hydrogen donors can have a mercapto group and an amino group at the same time.

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 may be 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 hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable,
Particularly, 2-mercaptobenzothiazole is preferable.

Next, the amine-based hydrogen donor can have at least one benzene ring or at least one heterocyclic ring.
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, 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 can be used. It is preferable to use them in combination in that the formed colored layer hardly falls off the substrate during development, and the strength and sensitivity of the colored layer 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'-bis (diethylamino) benzophenone, etc., and a more preferred combination is 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:
The ratio is from 1 to 1: 4, preferably from 1: 1 to 1: 3.

In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the amount used is preferably 0.01 to 40 parts by weight based on 100 parts by weight of all monomers in the radiation-sensitive composition. Parts, 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 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 resolution of the conductive path and the adhesion of the colored layer to the substrate are reduced. Tends to decrease.

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 (4)
(Hereinafter, referred to as “triazine-based compound (4)”)

[0057]

Embedded image

A compound represented by the following formula (5) (hereinafter referred to as
It is called "triazine compound (5)". )

[0059]

Embedded image

Examples of such compounds include a triazine compound having a halomethyl group.

Of these triazine compounds, 2-
[2- (3,4-dimethoxyphenyl) ethenyl]-
4,6-bis (trichloromethyl) -s-triazine,
Triazine compound (4), triazine compound (5)
Are preferred. The triazine compounds can be used alone or in combination of two or more.

In the present invention, when a triazine compound is used as a photopolymerization initiator, the amount used is preferably 0.01 to 40 parts by weight based on 100 parts by weight of all monomers in the radiation-sensitive composition. Parts, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. in this case,
When the use amount of the triazine-based compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a colored layer array in which the colored layer pattern is arranged according to a predetermined arrangement, On the other hand, if it exceeds 40 parts by weight, the resolution of the conduction path tends to decrease.

(E) Carboxyl group-containing monofunctional monomer The radiation-sensitive composition for a color liquid crystal display device of the present invention is characterized in that the (C) polyfunctional monomer is a carboxyl group-containing polyfunctional monomer. When the compound does not contain a carboxyl group-containing monomer having one polymerizable unsaturated bond, it preferably contains a carboxyl group-containing monofunctional monomer. When forming a colored layer from the composition, a conductive path of 5 μm or less can be formed in the colored layer. However, in the present invention, the carboxyl group-containing monofunctional monomer can also be used when the (C) polyfunctional monomer contains a carboxyl group-containing polyfunctional monomer. Also, when the carboxyl group-containing polyfunctional monomer and the carboxyl group-containing monofunctional monomer are combined to form a colored layer from the radiation-sensitive composition for a color liquid crystal display device, A conduction path of 5 μm or less can be formed. As the carboxyl group-containing monofunctional monomer, for example, in addition to the carboxyl group-containing unsaturated monomer exemplified for the alkali-soluble resin (B), mono [2- (meth) acryloyloxypropyl] succinate, phthalate Acid mono [2- (meth) acryloyloxypropyl] and the like can be mentioned.
Among these monofunctional monomers containing a carboxyl group, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxypropyl] succinate, and ω-carboxypolycaprolactone mono (meth) ) Acrylates and the like are preferred, and mono (2-acryloyloxyethyl) succinate is particularly preferred. Mono (2-acryloyloxyethyl) succinate can be obtained from M-5
It is commercially available under the trade name of 300 (manufactured by Toa Gosei Co., Ltd.). The carboxyl group-containing monofunctional monomers can be used alone or in combination of two or more.

In the present invention, the carboxyl group-containing monofunctional monomer further improves the solubility of the radiation-sensitive composition in an alkali developer and further suppresses the residual undissolved material after development. Etc., which fall under the category of an organic acid component as an additive described later. Among the carboxyl group-containing monofunctional monomers as the organic acid component, itaconic acid, citraconic acid, fumaric acid,
Monofunctional aliphatic dicarboxylic acids such as mesaconic acid are preferred compounds from the viewpoints of alkali solubility, solubility in a solvent described below, prevention of background fouling and film residue on a substrate and a light-shielding layer in an unexposed portion, and the like. .

In the present invention, the amount of the carboxyl group-containing monofunctional monomer used is usually 5 to 500 parts by weight, preferably 5 to 500 parts by weight, per 100 parts by weight of the alkali-soluble resin (B). 300 parts by weight, more preferably 1
0 to 150 parts by weight. In this case, if the use amount of the carboxyl group-containing monofunctional monomer is less than 5 parts by weight, depending on the composition of the radiation-sensitive composition (particularly, (C) the polyfunctional monomer may be When the conductive monomer is not contained), the formation of a required conductive path tends to be difficult. On the other hand, when it exceeds 500 parts by weight, depending on the composition of the radiation-sensitive composition (particularly, (C) When the reactive monomer contains a carboxyl group-containing polyfunctional monomer), for example, the alkali developability or the adhesion of the formed colored layer to the substrate is reduced, or the unexposed portion on the substrate or on the light-shielding layer , Soil contamination and film residue tend to occur easily.

In the present invention, when the carboxyl group-containing monofunctional monomer is used, the proportion of the monomer to the total monomer is usually 5 to 95% by weight, preferably 5 to 80% by weight, and more preferably 5 to 80% by weight. Is 5 to 50% by weight. In this case, the use ratio of the carboxyl group-containing monofunctional monomer is 5%.
If the content is less than 10% by weight, depending on the composition of the radiation-sensitive composition (particularly, when (C) the polyfunctional monomer does not contain a carboxyl group-containing polyfunctional monomer), the required conduction path may be reduced. On the other hand, when the content exceeds 95% by weight, the crosslinking density on the surface of the colored layer is reduced, and the alkali developing solution easily penetrates into the colored layer, and the surface of the colored layer is easily roughened during development. Or the colored layer tends to be missing during development.

Other Monofunctional Monomers Further, in the present invention, a part of (C) a polyfunctional monomer and / or (E) a carboxyl group-containing monofunctional monomer is partially replaced with another monofunctional monomer. It can be replaced by a functional monomer. Examples of the other monofunctional monomer include, for example, the copolymerizable unsaturated monomer exemplified for the (B) alkali-soluble resin, N-vinylsuccinimide, N-vinylpyrrolidone, N-vinylphthalimide, N-vinyl-2
-Piperidone, N-vinyl-ε-caprolactam, N-
Vinyl pyrrole, N-vinyl pyrrolidine, N-vinyl imidazole, N-vinyl imidazolidine, N-vinyl indole, N-vinyl indoline, N-vinyl benzimidazole, N-vinyl carbazole, N-vinyl piperidine, N-vinyl N-vinyl derivatives such as piperazine, N-vinyl morpholine, N-vinyl phenoxazine; N- (meth) acryloyl morpholine; and, as a commercial product, M-5600 (trade name, Toagosei Co., Ltd.)
Manufactured). These other monofunctional monomers can be used alone or in combination of two or more.

The proportion of the other monofunctional monomer to all the monomers is usually 90% by weight or less, preferably 50% by weight or less. In this case, when the use ratio of the other monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the pixel and the black matrix tend to decrease.

Additives The radiation-sensitive composition for a color liquid crystal display device of the present invention may contain various additives as necessary. Examples of the additive include an organic acid (provided that the carboxyl group-containing compound has an effect of further improving the solubility characteristics of the radiation-sensitive composition in an alkali developer and suppressing the remaining undissolved material after development). Examples thereof include a polyfunctional monomer and (E) excluding a carboxyl group-containing monofunctional monomer) or an organic amino compound (however, excluding the amine hydrogen donor).

-Organic acid- As the organic acid, an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in a molecule is preferable. Examples of the aliphatic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid, and cyclohexanecarboxylic acid; 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, cyclohexane-1,2-dicarboxylic acid,
Aliphatic dicarboxylic acids such as cyclohexane-1,3-dicarboxylic acid and cyclohexane-1,4-dicarboxylic acid;
Tricarballylic acid, aconitic acid, camphoronic acid, cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-
Examples thereof include aliphatic tricarboxylic acids such as 1,3,5-tricarboxylic acid.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group and compounds in which a carboxyl group is bonded to a phenyl group via a carbon chain. Examples of the phenyl group-containing carboxylic acid 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; benzene-1 , 2,3-
Trivalent or higher aromatic polycarboxylic acids such as tricarboxylic acid, trimellitic acid, trimesic acid, melophanic acid, and pyromellitic acid, phenylacetic acid, hydroatropic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamylidenic acid, and coumaric acid And umberic acid.

Of these organic acids, alkali solubility,
From the viewpoint of solubility in a solvent described below, prevention of background contamination and film residue on a substrate and a light-shielding layer on an unexposed portion,
As the aliphatic carboxylic acid, aliphatic dicarboxylic acids are preferable, and malonic acid and adipic acid are particularly preferable. 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 used is usually 15% by weight or less, preferably 10% by weight, based on the whole radiation-sensitive composition.
It is as follows. In this case, when the amount of the organic acid used exceeds 15% by weight, the adhesion of the formed colored layer to the substrate tends to decrease.

—Organic Amino Compound— The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule. 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, o-methylcyclohexylamine, m-methylcyclohexylamine, p-methylcyclohexylamine,
mono (cyclo) alkylamines such as o-ethylcyclohexylamine, m-ethylcyclohexylamine, p-ethylcyclohexylamine; methylethylamine;
Diethylamine, methyl n-propylamine, ethyl n
-Propylamine, di-n-propylamine, di-i-
Propylamine, di-n-butylamine, di-i-butylamine, di-sec-butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicyclohexyl Di (cyclo) such as amine
Alkylamines;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyln-propylamine, diethyln-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-
tri (cyclo) alkylamines such as n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine; 2-aminoethanol;
3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-
1-pentanol, 6-amino-1-hexanol, 4
Mono (cyclo) such as -amino-1-cyclohexanol
Alkanolamines; diethanolamine, di-n-
Propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine,
Di (cyclo) alkanolamines such as di-n-pentanolamine, di-n-hexanolamine, di (4-cyclohexanol) amine; triethanolamine;
Tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4-cyclohexanol) Tri (cyclo) alkanolamines such as amines;

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
Amino (cyclo) such as -dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, and 2-diethylamino-1,3-propanediol;
Alkanediols; 1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 3-dimethylaminocyclopentanemethanol, 3-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexane Methanol, 4
Amino-containing cycloalkane methanols such as diethylaminocyclohexanemethanol; β-alanine,
-Aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-
Aminocarboxylic acids such as aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid Acids and the like can be mentioned.

Examples of the phenyl group-containing amine include a compound in which an amino group is directly bonded to a phenyl group, a compound in which an amino group is bonded to a phenyl group via a carbon chain, and the like. Examples of the phenyl group-containing amine include aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, and p-ethylaniline.
n-propylaniline, pi-propylaniline, p
-N-butylaniline, pt-butylaniline, 1-
Naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-
Aromatic amines such as N, N-dimethylaniline; aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol; aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol; m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid; Examples include aminobenzoic acids (derivatives) such as p-diethylaminobenzoic acid.

Among these organic amino compounds, from the viewpoint of solubility in a solvent to be described later, prevention of background contamination and film residue on an unexposed portion on a substrate or a light-shielding layer, etc., aliphatic amines are mono (cyclo) amines. ) Alkanolamines, amino (cyclo) alkanediols are preferred,
In particular, 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 preferable, and as the phenyl group-containing amine, aminophenols are preferable, and o-amino is particularly preferable. Phenol, m-aminophenol, p-aminophenol and the like are preferred. The organic amino compounds can be used alone or in combination of two or more. The amount of the organic amino compound used is usually 1 to the entire radiation-sensitive composition.
It is at most 5% by weight, preferably at most 10% by weight. In this case, if the amount of the organic amino compound used exceeds 15% by weight, the adhesion of the formed colored layer to the substrate tends to decrease.

Other additives 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 and polyethylene glycol monoalkyl ethers. , High molecular compounds such as poly (fluoroalkyl acrylates); nonionic, cationic,
Surfactants such as anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl)-
3-aminopropyl methyl dimethoxysilane, N-
(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3
-Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-
Adhesion of (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Accelerator; 2,
Antioxidants such as 2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5 -UV absorbers such as chlorobenzotriazole and alkoxybenzophenones; Aggregation inhibitors such as sodium polyacrylate; 1,1'-azobis (cyclohexane-1-carbonitrile), 2-phenylazo-4-methoxy-2,4 -Thermal radical generators such as dimethylvaleronitrile.

Solvent The radiation-sensitive composition for a color liquid crystal display of the present invention is preferably prepared as a liquid composition by mixing a solvent. As the solvent, the components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components, and may be appropriately selected and used as long as they have appropriate volatility. it can. 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 ether,
(Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-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; diethylene glycol Jime Ethers, other ethers such as diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;

Methyl ethyl ketone, cyclohexanone,
Ketones such as 2-heptanone and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate and methyl 3-methoxypropionate; Ethyl 3-methoxypropionate, 3
-Methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-
Methyl-3-methoxybutyl acetate, 3-methyl-
3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate,
N-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Other esters such as ethyl; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide.

Of 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,
N-pentyl formate, i-pentyl acetate, n-propionate
-Butyl, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like are preferred. The solvents may be used alone or in combination of two or more.

Further, together with the solvent, 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.
The high boiling point 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 obtained radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is not limited. , Preferably 5 to 50% by weight, particularly preferably 10% by weight.
An amount of up to 40% by weight is desirable.

Method for Forming Colored Layer The radiation-sensitive composition for a color liquid crystal display device of the present invention comprises a driving substrate (hereinafter, referred to as “TFT”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed. It is used for forming a colored layer on a TFT type liquid crystal driving substrate by a lithography method. The coloring layer here means only a display pixel, only a black matrix, or a material containing both of them, and the coloring layer is a thin film transistor (TFT).
A color filter in a color liquid crystal display device or a component of the color filter. In the case where the formed colored layer includes a display pixel, a conductive path for conducting an electrode disposed on the colored layer and a terminal of a driving substrate below the colored layer, for example, a through hole Alternatively, a U-shaped depression is also formed.

Here, a method of forming a colored layer on a TFT type liquid crystal driving substrate will be described. In the case of forming a colored layer as a display pixel, on the surface of a TFT-type liquid crystal driving substrate, or on the surface of a substrate on which a passivation film such as a silicon nitride film is formed on the surface of the driving substrate,
If necessary, a light-shielding layer is formed so as to partition a portion where a pixel is formed, and then, on this substrate, for example, after applying a liquid composition of a radiation-sensitive composition in which a red pigment is dispersed,
Pre-baking is performed to evaporate the solvent to form a coating film. Next, after this coating film is exposed through a photomask, it is developed using an alkaline developer to dissolve and remove unexposed portions of the coating film, and then post-baked,
A pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed. The photomask used at that time includes
In addition to the pattern for forming the pixel, a pattern for forming the conduction path is also provided. Thereafter, using a liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, in the same manner as described above, application of each liquid composition,
Perform pre-bake, exposure, development and post-bake,
By forming a green pixel array and a blue pixel array on the same substrate, the three primary color pixel arrays of red, green and blue are arranged on a TFT type liquid crystal driving substrate and have a conductive path. Can be obtained. The size of the conductive path in the color liquid crystal display device thus formed is 5 μm or less, preferably 1 to 5 μm, depending on the corresponding pattern size of the photomask.
It can be appropriately selected in the range of m. Further, the black matrix can be formed in the same manner as in the case of the pixel array.

Examples of the substrate of the TFT type liquid crystal driving substrate used for forming the colored layer include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and the like. These substrates may be subjected to an appropriate pretreatment such as a chemical treatment with a silane coupling agent or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum deposition, if desired. When applying the liquid composition of the radiation-sensitive composition to the substrate,
Appropriate coating methods such as spin coating, casting coating, roll coating, and bar coating can be adopted. The coating thickness is preferably 0.1 to 10 μm, more preferably 0.2 to 5.0 μm, particularly preferably 0.2 to
3.0 μm. As the radiation used when forming the colored layer, for example, visible light, ultraviolet light, far ultraviolet light,
Electron beams, X-rays, etc. can be used,
Radiation in the range 0-450 nm is preferred. The exposure dose of radiation is preferably 10 to 10,000 J / m ² . Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, dimethylethanolamine, choline, and 1,8-diazabicyclo- [5.
4.0] -7-undecene, 1,5-diazabicyclo-
An aqueous solution such as [4.3.0] -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. After the alkali development, the film is usually washed with water.
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 5 to 3 at room temperature.
00 seconds is preferred.

The color liquid crystal display device provided with the color filter having the pixels and / or the black matrix formed as described above can be of a transmission type or a reflection type. The radioactive composition is also useful for a thin film transistor (TFT) type color image pickup tube element, a color sensor, and the like.

[0088]

BEST MODE FOR CARRYING OUT THE INVENTION The radiation-sensitive composition for a color liquid crystal display device of the present invention contains the above-mentioned components (A) to (D) as essential components. Preferred compositions are more specifically exemplified. Then, the following (a) to (nu) are performed. (A) A radiation-sensitive composition for a color liquid crystal display device in which (B) the alkali-soluble resin contains the carboxyl group-containing copolymer (I). (B) A radiation-sensitive composition for a color liquid crystal display device, wherein the carboxyl group-containing copolymer (I) is the carboxyl group-containing copolymer (II). (C) (C) The radiation-sensitive composition for a color liquid crystal display device according to the above (A) or (B), wherein part or all of the polyfunctional monomer is a carboxyl group-containing polyfunctional monomer. (D) The radiation-sensitive composition for a color liquid crystal display device according to (c) above, wherein the carboxyl group-containing polyfunctional monomer contains a polyfunctional acrylate (1) and / or a polyfunctional methacrylate (2). (E) (C) wherein the polyfunctional monomer contains at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate.
(B) The radiation-sensitive composition for a color liquid crystal display device according to (c) or (d). (F) (D) wherein the photopolymerization initiator comprises at least one selected from the group consisting of acetophenone-based compounds, biimidazole-based compounds, and triazine-based compounds;
(B) The radiation-sensitive composition for a color liquid crystal display device according to (c), (d) or (e). (G) (D) wherein the photopolymerization initiator contains a biimidazole-based compound and a hydrogen donor (A), (B), (C),
(D) or (E) the radiation-sensitive composition for a color liquid crystal display device. (H) The radiation-sensitive composition for a color liquid crystal display device according to (G) above, wherein (D) the photopolymerization initiator further comprises at least one selected from the group consisting of acetophenone-based compounds and triazine-based compounds. (I) The above (A), (B), (C), (D), and (D) further containing (E) a carboxyl group-containing monofunctional monomer.
(E), (F), (G) or (H), a radiation-sensitive composition for a color liquid crystal display device. (D) (A) The above (A), (B), (C), wherein the colorant contains an organic pigment and / or carbon black.
(D), (e), (f), (g), (h) or (li)
Radiation-sensitive composition for a color liquid crystal display device. Further, a preferred color liquid crystal display device according to the present invention includes: (l) a color filter having a colored layer formed from the radiation-sensitive composition for a color liquid crystal display device according to any one of (a) to (nu) above, It is arranged on a driving substrate of a (TFT) type color liquid crystal display device.

[0089]

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. / 25/35/10/1
5, Mw = 30,000, Mn = 10,000) 70 parts by weight, (C) 80 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer and 10 parts by weight of a polyfunctional acrylate (1), (D 2) As a photopolymerization initiator,
A liquid composition of a radiation-sensitive composition was prepared by mixing 50 parts by weight of benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent. Compound (R1) was prepared. <Formation and Evaluation of Pixel Array> Liquid Composition (R1)
Was applied using a spin coater on the surface of a TFT-type liquid crystal driving substrate on which a silicon nitride film was formed, and then pre-baked in a clean oven at 90 ° C. for 10 minutes to obtain a film thickness of 1 μm. A film having a thickness of 0.7 μm was formed. Then, after cooling the substrate to room temperature, the coating film was applied to a coating film of 365 nm, 4
UV light containing each wavelength of 05 nm and 436 nm
Exposure was performed at an exposure amount of 000 J / 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 red striped pixel array on the substrate. Observation of the obtained pixel array using an optical microscope revealed no development residue on the unexposed portion of the substrate. And 5μ
An m-square through hole was also opened, and the obtained pixel was excellent in adhesion to the substrate.

Example 2 (A) CI Pigment Red 177 and CI
100 parts by weight of a 65/35 (weight ratio) mixture of C.I. / 25/35/10/1
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) 2-methyl-1 as a photopolymerization initiator. 20 parts by weight of [4- (methylthio) phenyl] -2-morpholinopropanone-1, 15 parts by weight of 4,4'-bis (diethylamino) benzophenone as a sensitizer, and (E) a monofunctional monomer having a carboxyl group. As a monomer, 10 parts by weight of mono (2-acryloyloxyethyl) succinate and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent are mixed to obtain a liquid composition (R2) of a radiation-sensitive composition. Prepared. <Formation and Evaluation of Pixel Array> A red striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (R2) was used instead of the liquid composition (R1). Was evaluated. Observation of the obtained pixel array using an optical microscope revealed no development residue on the unexposed portion of the substrate. Moreover, a through hole of 5 μm square was also opened, and the obtained pixels were excellent in adhesion to the substrate.

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 and 10 parts by weight of a polyfunctional methacrylate (2), and (D) 2,2′-bis as a photopolymerization initiator. (2-chlorophenyl) -4,
6 parts by weight of 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 4,4′-amine as an amine hydrogen donor
A radiation-sensitive composition was prepared by mixing 6 parts by weight of bis (diethylamino) benzopheno, 3 parts by weight of 2-mercaptobenzothiazole as a mercaptan-based hydrogen donor, and 700 parts by weight of propylene glycol monomethyl ether acetate and 300 parts by weight of cyclohexanone as a solvent. (B1) was prepared. <Formation and Evaluation of Pixel Array> A blue striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (B1) was used instead of the liquid composition (R1). Was evaluated. Observation of the obtained pixel array using an optical microscope revealed no development residue on the unexposed portion of the substrate. Moreover, a through hole of 5 μm square was also opened, and the obtained pixels were excellent in adhesion to the substrate.

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 and 10 parts by weight of a polyfunctional acrylate (1), and (D) a triazine compound (4) as a photopolymerization initiator. 10 parts by weight, 700 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 300 parts by weight of cyclohexanone were mixed to prepare a liquid composition (G1) of a radiation-sensitive composition. <Formation and Evaluation of Pixel Array> A green striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (G1) was used instead of the liquid composition (R1). Was evaluated. Observation of the obtained pixel array using an optical microscope revealed no development residue on the unexposed portion of the substrate. Moreover, a through hole of 5 μm square was also opened, and the obtained pixels were excellent in adhesion to the substrate.

[0093]

According to the radiation-sensitive composition for a color liquid crystal display device of the present invention, a conductive path of 5 μm or less, particularly a through hole or a U-shaped depression can be formed in the colored layer when the colored layer is formed. There is no development residue at the time of development, and the adhesiveness with a TFT type liquid crystal driving substrate and a passivation film such as a silicon nitride film is excellent.
Therefore, the radiation-sensitive composition for a color liquid crystal display device of the present invention can provide a high definition and high quality color liquid crystal display device having a high aperture ratio.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/1335 505 G02F 1/1335 505 G09F 9/33 G09F 9/33 Y (72) Inventor Takeshi Watanabe Tokyo 2-11-24 Tsukiji, Chuo-ku, Tokyo F-term (reference) within JSR Co., Ltd. 4J026 AA17 AA19 AA20 AA31 AA37 AA38 AA43 AA44 AA45 AA46 AA47 AA48 AA49 AA53 AA54 AA56 AA57 AA59 AA62 AA68 AA69 AA71 AA72 AA76 AC17 AC18 AC23 BA26 BA27 BA28 BA30 ABA DBA DBA DBA DBA CA24 DA13 FB01 FB20 JA08

Claims (5)

[Claims] 1. A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator, wherein a colored layer is formed. A radiation sensitive color liquid crystal display device used for forming a colored layer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, which can sometimes form a conduction path of 5 μm or less with respect to the colored layer. Composition. 2. A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, wherein (C) A colored layer is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, wherein a part or all of the polyfunctional monomer is composed of a carboxyl group-containing polyfunctional monomer. Radiation-sensitive composition for a color liquid crystal display device used for the same. 3. The thin film transistor according to claim 2, wherein the carboxyl group-containing polyfunctional monomer contains a compound represented by the following formula (1) and / or a compound represented by the following formula (2). A radiation-sensitive composition for a color liquid crystal display device used for forming a colored layer on a driving substrate of a TFT) type color liquid crystal display device. Embedded image Embedded image 4. It contains (A) a coloring agent, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photopolymerization initiator, and (E) a carboxyl group-containing monofunctional monomer. A radiation-sensitive composition for a color liquid crystal display device used for forming a colored layer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. 5. A color filter having a colored layer formed from the radiation-sensitive composition for a color liquid crystal display device according to claim 1, wherein the color filter is a thin film transistor (TF).
T) A color liquid crystal display device which is arranged on a driving substrate of a color liquid crystal display device.