JP2002040225A - Radiation sensitive composition for color liquid crystal display device and color liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive composition for a color liquid crystal display device which is used to form a color layer on a driving substrate of a color liquid crystal display device with a thin film transistor(TFT) method and which shows such properties that no seizure of an image is caused during operating the display panel, conducting paths of <=5 μm length can be formed, no development residue is produced during development and excellent adhesion property with the driving substrate or a passivation film is obtained. SOLUTION: The radiation sensitive composition for a color liquid crystal display device contains (A) pigments, (B) dispersant, (C) alkali soluble resin (D) polyfunctional monomers and (E) photopolymerization initiator. The extracted amount of the caprolacton component in a color layer formed from the above composition by acetonitrile is <=5 wt.% of the color layer. The composition is to be used to form a color layer on the driving substrate of a color liquid crystal display device with a thin film transistor(TFT) method.

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 and a color liquid crystal display.

[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 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. A method has been developed in which a substrate is bonded to a substrate on which an ITO (tin-doped indium oxide) electrode is formed by sputtering. 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. However, when the colored layer is formed by the latter method, image sticking tends to occur during operation of the display panel, which is a serious problem. The cause may be impurities that seep into the liquid crystal from the colored layer, but the type of the corresponding impurities is not always clear, and the evaluation criteria for effectively preventing image sticking are also unclear. Is an important issue. In addition, the colored layer formed by this method has a structure in which an ITO electrode disposed on the colored layer is electrically connected to a terminal of a driving substrate below the colored layer.
Although it is necessary to form a conductive path such as a rectangular through hole or a U-shaped depression having a length of about 1 to 15 μm, preferably 5 μm or less, a conventional thin film transistor (TFT) type color liquid crystal display device is required. In the radiation-sensitive composition used for forming the colored layer on the driving substrate, the conductive path of 5 μm or less could not be formed.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to prevent image sticking when a display panel is operated.
In addition, a conductive path of 5 μm or less can be formed, no development residue occurs during development, and excellent adhesion to a driving substrate on which a thin film transistor (TFT) is disposed or a passivation film such as a silicon nitride film. Another 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 thin film transistor (TFT) type color liquid crystal display device.

[0004]

According to the present invention, the object is to provide (A) a pigment, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer and (E) A radiation-sensitive composition for a color liquid crystal display device containing a photopolymerization initiator, wherein the amount of a caprolactone component extracted by acetonitrile from a colored layer formed from the composition is 5% of the colored layer.
It 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, characterized in that the content is not more than weight%. . The “caprolactone component” in the present invention means caprolactone, a caprolactone derivative, or a mixture of two or more thereof. The term “radiation” as used in the present invention means those including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

The inventors of the present invention have conducted intensive studies on impurities causing image sticking during operation of the display panel and evaluation criteria that can effectively prevent image sticking.
The caprolactone component that seeps into the liquid crystal from the colored layer is a major cause of image sticking,
The present inventors have found that by setting the amount of the caprolactone component extracted by acetonitrile in the coloring layer to 5% by weight or less of the coloring layer, image sticking can be effectively prevented, and the present invention has been accomplished. Therefore, it is preferable that the content of the caprolactone component is “zero” or as small as possible for all the components constituting the radiation-sensitive composition for a color liquid crystal display device of the present invention, in particular, for the dispersant (B). . In this case, examples of the caprolactone derivative in the caprolactone component include methyl-substituted caprolactone, oligomers of caprolactone and methyl-substituted caprolactone (polymerization degree is, for example, 4 or less).

Hereinafter, the present invention will be described in detail. (A) Pigment The pigment in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter. Since the color filter is required to have high-definition color development and heat resistance, as the pigment in the present invention, a pigment having a high color development property and a high heat resistance, particularly a pigment having a high thermal decomposition resistance is preferable, and an organic pigment is preferable. And / or carbon black is used.

Examples of the organic pigment include a color index (CI; The Society of Dyers and Coloris).
Compounds which are classified as Pigment (published by ts Co., Ltd.), specifically, those having the following color index (CI) numbers. 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.
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;

[0009] 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 the 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 pigment, and the organic pigment is used for forming a black matrix. If so, preferably two or more organic pigments and / or carbon black are used as pigments. In the present invention, a dye or a natural pigment can be used together with the pigment, as the case requires.

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

(B) Dispersant The dispersant in the present invention is a component having the function of uniformly dispersing the (A) pigment in the radiation-sensitive composition. Examples of such dispersants include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based dispersants. Examples of the dispersant include a dispersant having a urethane bond (hereinafter, “urethane-based dispersant”).
That. Polyethyleneimine-based dispersants; polyoxyethylene alkyl ether-based dispersants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n- Polyoxyethylene alkyl phenyl ether dispersants such as nonylphenyl ether; polyethylene glycol diester dispersants such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid ester dispersants; and fatty acid-modified polyester dispersants. Can be.
Among these dispersants, urethane dispersants are particularly preferable. The urethane-based dispersant contains no or very little caprolactone component that causes image sticking. Commercial products of the preferred dispersant include, for example, Disperbyk (manufactured by BYK Japan KK), EFKA (manufactured by EFKA Chemicals), Dispalon (manufactured by Kusumoto Chemicals), and the like. In the present invention, the dispersants can be used alone or in combination of two or more.

The amount of the dispersant used in the present invention is (A)
0.5 to 100 parts by weight, preferably 1 to 70 parts by weight, particularly preferably 10 to 100 parts by weight, based on 100 parts by weight of the pigment.
50 parts by weight. In this case, the amount of the dispersant used is 0.5
If the amount is less than 100 parts by weight, good dispersibility of the pigment (A) may not be secured. If the amount is more than 100 parts by weight, developability and the like may be impaired.

In the present invention, a dispersing aid can be used in combination with the dispersing agent. Examples of the dispersion aid include a copper phthalocyanine sulfonic acid compound. Specific examples of the copper phthalocyanine sulfonic acid compound include copper phthalocyanine sulfonic acid, copper phthalocyanine sulfonic acid ammonium, copper phthalocyanine sulfonic acid tetramethyl ammonium, copper phthalocyanine sulfonic acid tetraethyl ammonium, copper phthalocyanine sulfonic acid tetra-n-propyl ammonium, copper Examples thereof include tetra-i-propyl ammonium phthalocyanine sulfonate and tetra-n-butyl ammonium copper phthalocyanine sulfonate. These copper phthalocyanine sulfonic acid compounds can be used alone or in combination of two or more. The amount of the dispersing aid to be used is generally 20 parts by weight or less, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the pigment (A).

(C) Alkali-Soluble Resin As the alkali-soluble resin in the present invention, (A) a developer which acts as a binder for the pigment and is used in the development step of the color filter at the time of producing the color filter, especially The polymerizable unsaturated monomer having an acidic functional group such as a carboxyl group, a phenolic hydroxyl group and a sulfonic acid is not particularly limited as long as it is preferably soluble in an alkali developing solution. And other copolymerizable unsaturated monomers (hereinafter, referred to as "copolymerizable unsaturated monomers").

Examples of the polymerizable unsaturated monomer having a carboxyl group (hereinafter, referred to as “carboxyl group-containing unsaturated monomer”) include (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 terminals, such as ω-carboxypolycaprolactone mono (meth) acrylate. Among these carboxyl group-containing unsaturated monomers, (meth) acrylic acid and succinic acid mono [2-
(Meth) acryloyloxyethyl] and the like. The unsaturated monomers having a carboxyl group may be used alone or in combination of two or more.

Examples of the polymerizable unsaturated monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-styrene. α-methylstyrene, p-hydroxy-α-methylstyrene, No-hydroxyphenylmaleimide,
Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide and the like can be mentioned. These polymerizable unsaturated monomers having a phenolic hydroxyl group can be used alone or in combination of two or more. Examples of the polymerizable unsaturated monomer having a sulfonic acid group include isoprenesulfonic acid and p-styrenesulfonic acid. These polymerizable unsaturated monomers having a sulfonic acid group can be used alone or in combination.
A mixture of more than one species can be used.

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 (1)

[0022]

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

Unsaturated carboxylic acid 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, 2-
Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate, and 3-dimethylaminopropyl (meth) acrylate; glycidyl (meth) acrylate and the like Unsaturated carboxylic acid glycidyl esters; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; unsaturated amides such as (meth) acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide And conjugated dienes such as 1,3-butadiene, isoprene and chloroprene.

Of 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 monomer,
They can be used alone or in combination of two or more.

As a preferred 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, and particularly,
A carboxyl group-containing unsaturated monomer component containing (meth) acrylic acid as an essential component and optionally further containing mono [2- (meth) acryloyloxyethyl] succinate;
Polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide,
At least one selected from the group consisting of N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate, and optionally styrene, methyl (meth) acrylate, allyl ( A copolymer of a monomer mixture further containing at least one member selected from the group consisting of meth) acrylate and phenyl (meth) acrylate (hereinafter referred to as “carboxyl group-containing copolymer (I
I) ". Is preferred.

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, the coloring layer tends to fall off from the substrate and the coloring layer surface tends to be rough.

The alkali-soluble resin of 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 contamination, film residue, and the like hardly occur on the substrate in the non-irradiated portion and on the light shielding layer. Further, the ratio of Mw to Mn of the alkali-soluble resin (M
(w / Mn) is usually 1 to 5, preferably 1 to 4. In the present invention, the alkali-soluble resins can be used alone or in combination of two or more.

The amount of the alkali-soluble resin used in the present invention is usually 10 to 10 parts by weight of the pigment (A).
It is 1,000 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 substrate or the light-shielding layer of the non-irradiated portion, On the other hand, when the amount exceeds 1,000 parts by weight, the pigment concentration relatively decreases, so that it may be difficult to achieve a target color density as a thin film.

(D) Polyfunctional Monomer The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds. Examples of the polyfunctional monomer include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; di (meth) acrylates of polyalkylene glycol such as polyethylene glycol and polypropylene glycol; glycerin and trimethylol Poly (meth) acrylates 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. Oligo (meth) acrylates; di (meth) acrylates of hydroxyl-terminated polymers such as hydroxy-terminated poly-1,3-butadiene, hydroxy-terminated polyisoprene, hydroxy-terminated polycaprolactone Rate such or can include tris [2- (meth) acryloyloxyethyl] phosphate and the like.

Of these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and modified products of dicarboxylic acids thereof are preferred. Specifically, trimethylolpropanetri (meth) acrylate Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, the following formula (2)

[0034]

Embedded image [In the formula (2), each R ² independently represents a hydrogen atom or a methyl group. ]

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 in the non-irradiated portion of the substrate. This is preferable in that background soiling, film residue, and the like hardly occur on the upper and light-shielding layers. These polyfunctional monomers can be used alone or in combination of two or more.

The amount of the polyfunctional monomer used in the present invention is based on 100 parts by weight of the alkali-soluble resin (C).
Usually, it is 5 to 300 parts by weight, preferably 70 to 300 parts by weight, particularly preferably 100 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 colored layer tend to decrease, while 3
When the amount is more than 00 parts by weight, for example, alkali developability tends to decrease, and background contamination or film residue tends to be easily generated on the substrate or the light shielding layer in the non-irradiated portion. In the present invention, from the viewpoint of reliably preventing image sticking, as long as other functions of the color liquid crystal display device are not impaired, it is preferable that the amount of the polyfunctional monomer used is larger in the above range.

In the present invention, a part of the polyfunctional monomer can be replaced by a monofunctional monomer having one polymerizable unsaturated bond. Examples of the monofunctional monomer include carboxyl group-containing unsaturated monomers and copolymerizable unsaturated monomers exemplified for the (B) alkali-soluble resin, N-vinylsuccinimide, and N-vinyl. Pyrrolidone, 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 -Vinylcarbazole, N-vinylpiperidine, N-vinylpiperazine, N-vinylmorpholine,
N-vinyl derivatives such as N-vinylphenoxazine;
In addition to (meth) acryloylmorpholine, commercially available products include M-5300, M-5400, and M-5600 (trade name, manufactured by Toagosei Co., Ltd.). These monofunctional monomers can be used alone or in combination of two or more. The proportion of the monofunctional monomer used is usually 50% by weight or less, preferably 30% by weight or less, particularly preferably 10% by weight, based on the total of the polyfunctional monomer and the monofunctional monomer. Part or less. in this case,
When the use ratio of the monofunctional monomer exceeds 50% by weight, the strength and the surface smoothness of the colored layer tend to decrease, and the cross-linking density of the obtained pixel decreases, and the image sticking of the image in the present invention decreases. May have an adverse effect on the prevention effect.

(E) Photopolymerization Initiator The photopolymerization initiator in the present invention is obtained by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray (hereinafter, referred to as “exposure”), and the above-mentioned (photoexposure). D) Compounds capable of generating active species capable of initiating the polymerization of polyfunctional monomers and optionally used monofunctional monomers. Such photopolymerization initiators include, for example, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, benzoin-based compounds, benzophenone-based compounds, α
-Diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds and the like. 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.

The general amount of the photopolymerization initiator used in the present invention is usually from 0.01 to 100 parts by weight of the total of (D) the polyfunctional monomer and the monofunctional monomer. 80 parts by weight, preferably 1 to 60 parts by weight. In this case, if the 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 pixel array in which a pixel pattern is arranged according to a predetermined arrangement, On the other hand, if it exceeds 80 parts by weight, the formed colored layer tends to fall off the substrate during development.

Among the preferred photopolymerization initiators in the present invention, specific examples of acetophenone compounds 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-based compounds, in particular, 2-methyl-1-
[4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl) butanone-1 is preferred. The acetophenone compounds can be used alone or in combination of two or more.

In the present invention, when an acetophenone compound is used as a photopolymerization initiator, the amount used is (D)
Usually, 0.01 to 80 parts by weight, preferably 1 to 100 parts by weight of the total of the polyfunctional monomer and the monofunctional monomer.
６０60 parts by weight, more preferably 1-30 parts by weight. In this case, the amount of the acetophenone-based compound to be used is 0.1.
If the amount is less than 01 parts by weight, curing by exposure becomes insufficient,
It may be difficult to obtain a pixel array in which the pixel patterns are arranged in accordance with a predetermined arrangement. On the other hand, if it exceeds 80 parts by weight, the formed colored layer tends to fall off the substrate during development.

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.

Of 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'-tetraphenyl −
1,2′-biimidazole and the like are preferred, and
2'-bis (2,4-dichlorophenyl) -4,4 ',
5,5′-Tetraphenyl-1,2′-biimidazole is preferred. The biimidazole-based compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved substances and precipitates, and has high sensitivity. Since the curing reaction is high and no curing reaction occurs in the unexposed area, the coated film after exposure is clearly divided into a cured area insoluble in the developer and an uncured area having a high solubility in the developer. It is possible to form a high-definition pixel array in which the pixel patterns are divided, and pixel patterns without undercuts are arranged according to a predetermined arrangement. 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 a photopolymerization initiator, the amount used is (D)
Usually, 0.01 to 40 parts by weight, preferably 1 to 100 parts by weight of the total of the polyfunctional monomer and the monofunctional monomer.
-30 parts by weight, particularly preferably 1-20 parts by weight.
In this case, the amount of the biimidazole compound used is 0.01%.
If the amount is less than 10 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a pixel array in which the pixel pattern is arranged according to a predetermined arrangement. There is a tendency that the colored layer falls off the substrate and the film on the surface of the colored layer is easily damaged.

-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 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.

The hydrogen donor is preferably a mercaptan compound or an amine compound defined below.
The mercaptan compound has a benzene ring or a heterocyclic ring as a mother nucleus, and has a mercapto group directly bonded to the mother nucleus as one.
Or more, preferably 1 to 3, more preferably 1 to 2
Compound (hereinafter referred to as "mercaptan hydrogen donor")
That. ). 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 donor "). 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 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 a mercaptan-based hydrogen donor include 2-mercaptobenzothiazole and 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.

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, 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 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 (D) 100 parts by weight of the total of 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 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 colored layer falls off the substrate during development. Tend to be easier.

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)
Triazine compounds having a halomethyl group such as -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine are exemplified. be able to.
Among these triazine compounds, 2- [2- (3,
4-Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine and the like 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 based on 100 parts by weight of the total of (D) 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, the amount of the triazine compound used is 0.0
If the amount is less than 1 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a pixel array in which pixel patterns are arranged according to a predetermined arrangement.
If the amount exceeds the weight part, the formed colored layer tends to easily fall off the substrate during development.

Additives The radiation-sensitive composition for a color liquid crystal display device of the present invention can contain various additives as necessary. Examples of the additive include an organic acid or an organic amino compound (however, an organic acid or an organic amino compound that further improves the solubility characteristics of the radiation-sensitive composition in an alkali developer and has an effect of further suppressing the remaining of undissolved material after development). Excluding the 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 acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, and 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,
Aliphatic dicarboxylic acids such as methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid;
Examples thereof include aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include a compound in which a carboxyl group is directly bonded to a phenyl group and a compound 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.

Among these organic acids, alkali solubility,
As the aliphatic carboxylic acid, aliphatic dicarboxylic acids are preferable, and in particular, malonic acid and adipine, from the viewpoints of solubility in a solvent described below, prevention of background contamination and film residue on a substrate or a light-shielding layer in an unexposed portion, and the like. Acids, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, and the like are preferred. As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferred, and phthalic acid is particularly preferred. The organic acids can be used alone or in combination of two or more. The amount of the organic acid to be used is generally 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. 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, 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-sec-butylamine, tri-t-butylamine, tri- n-pentylamine, tri-n-hexylamine,
Tri (cyclo) alkylamines such as dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;

2-aminoethanol, 3-amino-1-
Propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-
Mono (cyclo) alkanolamines such as cyclohexanol; diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, Di-n-hexanolamine, di (4-
Di (cyclo) alkanolamines such as cyclohexanol) amine; triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-amine Tri (cyclo) alkanolamines such as pentanolamine, tri-n-hexanolamine and tri (4-cyclohexanol) amine;

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, 2-diethylamino-1,3-propanediol
Alkanediols; 1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-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 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, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, and p-ethylaniline.
n-propylaniline, p-i-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 fouling and film residue on a substrate or a light-shielding layer in an unexposed portion, aliphatic amines such as mono (cyclo) ) Alkanolamines and amino (cyclo) 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 preferable, and as the phenyl group-containing amine,
Aminophenols are preferred, and o-aminophenol, m-aminophenol, p-aminophenol and the like are particularly preferred. The organic amino compound may be used alone or
A mixture of more than one species can be used. The amount of the organic amino compound used is usually based on the entire radiation-sensitive composition.
It is at most 15% 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. , Poly (fluoroalkyl acrylates) and other high molecular compounds; 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 device of the present invention comprises the (A) pigment, (B) dispersant, (C) alkali-soluble resin, (D) polyfunctional monomer and (E) ) A photopolymerization initiator is an essential component, but is preferably prepared as a liquid composition by mixing a solvent. As the solvent, a component which disperses or dissolves the components (A) to (E) and the additive component constituting the radiation-sensitive composition, does not react with these components, and has 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, diethylene glycol mono-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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (Such as propylene glycol monoethyl ether) I) alkylene glycol monoalkyl ethers; (poly) 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, propylene glycol monoethyl ether acetate, and the like. Alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Methyl propionic acid,
Lactic acid alkyl esters such as ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, 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-other esters such as oxobutanoate ethyl; toluene, xylene and the like aromatic hydrocarbons; N- methylpyrrolidone, N, N-dimethylformamide, N,
Examples thereof include amides such as N-dimethylacetamide.

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, from the viewpoint of solubility, pigment dispersibility, coatability and the like.
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, benzyl ethyl ether, dihexyl ether, acetonylacetone,
Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate , Etc. can 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 1 to 50% by weight.
An amount of 0 to 40% by weight is desirable.

Method for Forming a 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 referred to here means only a display pixel, only a black matrix, or a layer containing both of them. Here, a method for forming a colored layer on a TFT type liquid crystal driving substrate will be described. First, a portion where a pixel is to be formed is formed, if necessary, on the surface of a TFT 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. A light-shielding layer is formed on the substrate, for example, after applying a liquid composition of a radiation-sensitive composition in which, for example, a red pigment is dispersed, performing a pre-bake to evaporate a 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 the unexposed portions of the coating film, and then post-baked, so that a red pixel pattern is formed in a predetermined manner. A pixel array arranged in an array is formed. The photomask used at this time is provided with a pattern for forming a conduction path such as a through hole or a U-shaped depression, in addition to a pattern for forming a pixel. 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, applying, pre-baking, exposing, developing and post-baking each liquid composition to obtain a green color By forming the pixel array and the blue pixel array on the same substrate, the three primary color pixel arrays of red, green and blue are arranged on the TFT type liquid crystal driving substrate,
In addition, a color liquid crystal display device having a conduction path can be obtained. Further, the black matrix can be formed in the same manner as in the case of the pixel array.

Examples of the substrate in 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,
An appropriate coating method such as spin coating, casting coating, and roll coating can be employed. The coating thickness is preferably 0.1 to 10 μm, more preferably 0.2 to 5.0 μm, and particularly preferably 0.2 to 3.0 μm, as the thickness after drying.
m. As the radiation used when forming the colored layer, for example, visible light, ultraviolet light, far ultraviolet light, electron beam,
X-rays and the like can be used, but the wavelength is 190-45.
Radiation in the range of 0 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- [4.
3.0] -5-nonene and the like. 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 condition is preferably at room temperature for 5 to 300 seconds.

The amount of the caprolactone component extracted by acetonitrile in the colored layer formed from the radiation-sensitive composition for a color liquid crystal display device of the present invention is 5% by weight or less, preferably 3% by weight or less of the colored layer. In the present invention, by extracting the caprolactone component in the colored layer with acetonitrile at 5% by weight or less of the colored layer,
In particular, it is possible to obtain a color liquid crystal display device that does not cause image sticking when the display panel is operated. The measurement of the amount of the caprolactone component extracted by acetonitrile of the colored layer in the present invention was performed by forming a colored layer on a suitable substrate in accordance with the conditions for forming a colored layer for a color liquid crystal display from the radiation-sensitive composition of the present invention. Thereafter, a test piece of a colored layer was scraped off from the substrate, and the test piece 100
mg of acetonitrile was sufficiently mixed with 10 cc of acetonitrile at room temperature, and then filtered to remove insoluble components. The amount of the caprolactone component in the obtained "filtrate" was analyzed by gas chromatography (elution solvent: tetrahydrofuran). It is implemented by. The substrate used in this case does not necessarily need to be the same as the substrate for the color liquid crystal display device, and the mixing conditions such as the shape of the test piece and the mixing method and mixing time are determined by the caprolactone component contained in the test piece. Is not particularly limited as long as it can be extracted with acetonitrile.

The color liquid crystal display having a colored layer formed from the radiation-sensitive composition for a color liquid crystal display of the present invention can be of a transmission type or a reflection type. The radiation-sensitive composition is also useful for a thin film transistor (TFT) type color image pickup tube element, a color sensor, and the like.

[0074]

BEST MODE FOR CARRYING OUT THE INVENTION The radiation-sensitive composition for a color liquid crystal display device of the present invention comprises the pigment (A), the dispersant (B) and the dispersant (B), the alkali-soluble resin (C), and the polyfunctional (D). A reactive monomer and (E) a photopolymerization initiator as essential components,
The amount of the caprolactone component extracted by acetonitrile in the colored layer formed from the composition is 5% by weight of the colored layer.
It is characterized by the following, but specific examples of preferred compositions are as follows (a) to (h). (A) A radiation-sensitive composition for a color liquid crystal display device in which (C) 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) (D) wherein the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate.
Or (b) the radiation-sensitive composition for a color liquid crystal display device. (D) (E) wherein the photopolymerization initiator contains at least one selected from the group consisting of an acetophenone-based compound, a biimidazole-based compound, and a triazine-based compound;
The radiation-sensitive composition for a color liquid crystal display device according to (b) or (c). (E) (E) The radiation-sensitive composition for a color liquid crystal display device of (A), (B) or (C), wherein the photopolymerization initiator contains a biimidazole compound and a hydrogen donor. (F) The radiation-sensitive composition for a color liquid crystal display device according to (e), wherein (E) the photopolymerization initiator further comprises at least one selected from the group consisting of an acetophenone-based compound and a triazine-based compound. (G) (A) The above (A), (B), (C), (D), wherein the pigment contains an organic pigment and / or carbon black.
(E) or (f), the radiation-sensitive composition for a color liquid crystal display device. (H) The extraction amount of a caprolactone component by acetonitrile of the colored layer formed from the radiation-sensitive composition for a color liquid crystal display device is preferably 3% by weight or less of the colored layer, wherein (a), (b), (C), (d), (e),
(F) or (g) the radiation-sensitive composition for a color liquid crystal display device.

Further, a preferred color liquid crystal display device of the present invention has a structure in which a colored layer is formed directly or via a passivation film on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. Wherein the colored layer is (a), (b), (c), (d), (e),
(F), (g) or (h) formed from the radiation-sensitive composition for a color liquid crystal display device.

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. The measurement and evaluation in Examples and Comparative Examples were performed as follows. Measurement of extraction amount of caprolactone component Each liquid composition was applied using a spin coater on the surface of a substrate on which a silicon nitride film was formed on the surface of a TFT-type liquid crystal driving substrate, and then applied in a 90 ° C. clean oven. For 10 minutes to form a coating film having a thickness of 5.0 μm. Then, after cooling the substrate to room temperature, the coated film was coated with a high-pressure mercury lamp through a photomask.
Ultraviolet rays having wavelengths of 65 nm, 405 nm and 436 nm were exposed at an exposure amount of 5,000 J / m ² to form a colored layer (continuous film). Thereafter, 100 mg of the coloring layer was scraped off from the substrate to form a test piece, and the test piece was mixed with 10 cc of acetonitrile, and ultrasonic waves were applied for 15 minutes.
After shaking for another 30 minutes, it was left for one day. Thereafter, ultrasonic waves were further applied for 15 minutes, the mixture was filtered through a filter having a pore size of 1 μm, insolubles were filtered off, and the filtrate was analyzed by gas chromatography (elution solvent: tetrahydrofuran) to extract the caprolactone component. Was measured.

Evaluation of Burn-in Liquid Crystal: A nematic liquid crystal (trade name: ZLI-5081, manufactured by Merck Japan Ltd.) composed of a fluorobiphenyl derivative was used. Production of liquid crystal display element: 1 cm ² patterned on one side of a glass substrate
After forming an ITO film, a commercially available liquid crystal aligning agent for an active matrix is applied on the ITO film by using a spinner, and then dried at 180 ° C. for 1 hour to obtain a film having a thickness of 6 μm.
A 00 ° coating was formed. After a patterned 1 cm ² ITO film was formed on a color filter formed using the liquid composition of each comparative example, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. . After a patterned 1 cm ² ITO film was formed on a color filter formed using the liquid composition of each example, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. . After forming an ITO film (continuous film) on one side of a glass substrate, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. Next, a rubbing treatment was performed on the surface of the coating film on each substrate obtained by using a rubbing machine provided with a roll wound with a rayon cloth to form a liquid crystal alignment film. The rubbing condition at that time was a roll rotation speed of 400
rpm, the stage movement speed was 3 cm / sec, and the push-in length of the hair foot was 0.4 mm. Of the substrates on which the liquid crystal alignment film has been formed in this way, or each of the substrates that have been subjected to the processing, are combined with the substrates that have been subjected to the processing to form a set of two substrates. After applying an epoxy resin-based adhesive containing a silica gel columnar spacer with a diameter of 5.5 μm to the part by screen printing, the gap between the two substrates is adjusted so that the rubbing directions of the liquid crystal alignment films cross at 90 degrees. The substrates were opened and opposed to each other, and were pressed so that the outer edges of the substrates were in contact with each other to cure the adhesive. Next, for each set, a nematic liquid crystal “ZLI-5081” is injected and filled into a cell gap defined by an inner surface of two substrates and a cured layer of an adhesive, and then the injection hole is sealed. A liquid crystal cell was manufactured. Thereafter, a polarizing plate was attached to the outer surface of the liquid crystal cell so that the polarization direction of the polarizing plate coincided with the rubbing direction of the liquid crystal alignment film on each substrate, thereby producing a liquid crystal display device.

Evaluation method for burn-in: Function generator WAVE
A FACTRY (manufactured by NF ELECTRONIC INSTRUMENT) is connected, a rectangular wave voltage of AC 3 V and DC 1 V is applied, and the liquid crystal display element is heated at 70 ° C. for 1 hour in that state. After heating the liquid crystal display element, cut off the square wave voltage
After allowing to cool for 30 minutes, a rectangular wave voltage of 30 Hz and a halftone voltage is applied by the function generator. Using LCD EVALUATION SYSTEM (Photal),
The flicker waveform obtained from the flicker appearance pulse data related to the display of the liquid crystal display element is converted to an oscilloscope 54.
600A OSCILLOSCOPE (manufactured by HEWLETT PACKARD), FFT analyzer R9211C FFT SERVO ANALYZER (ADV
ANTEST) to measure flicker strength. An offset voltage is applied by the function generator, and an offset voltage at a point where the flicker waveform completely disappears is measured to obtain a flicker elimination voltage (that is, a burn-in removal voltage). The degree of burn-in increases as the flicker elimination voltage increases. If the flicker elimination voltage is less than 50 mV, burn-in does not occur, but if it is 50 mV or more, burn-in occurs. Here, the case where the flicker elimination voltage is less than 10 mV, the burn-in is “excellent”, the case of 10 mV or more and less than 50 mV, the burn-in is “good”, and the case of 50 mV or more is “bad”.

Comparative Example 1 (A) 80 parts by weight of CI Pigment Green 7 as a pigment, (B) 12 parts by weight of a polyethyleneimine dispersant (trade name: Solsperse 24000) as a dispersant, and (C) (meth) as an alkali-soluble resin Acrylic acid / mono [2- (meth) acryloyloxyethyl] succinate / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer (copolymerization weight ratio = 15/25/35/10 /
15, Mw = 30,000, Mn = 10,000) 10
0 parts by weight, (D) 50 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (E) 2-benzyl-2-dimethylamino-1- as a photopolymerization initiator.
A liquid composition (g1) of a radiation-sensitive composition was prepared by mixing 50 parts by weight of (4-morpholinophenyl) butanone-1 and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent.

A liquid composition (g1) for forming a pixel array is applied on a surface of a TFT type liquid crystal driving substrate on which a silicon nitride film is formed by using a spin coater, and then a 90 ° C. clean liquid is applied. Pre-baking was performed in an oven for 10 minutes to form a coating film having a thickness of 2 μm. Then, after cooling the substrate to room temperature,
Using a high-pressure mercury lamp, the coating film was exposed to ultraviolet light having a wavelength of 365 nm, 405 nm and 436 nm through a photomask at an exposure amount of 2,000 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. Then 220 ° C
Was performed in a clean oven for 25 minutes to form a green striped pixel array on the substrate.

[0081] When a pixel array obtained evaluation was observed using an optical microscope, also through hole 5μm angles are open, the developer left on the substrate in the unexposed portion was not observed, and the substrate of the pixel Was also excellent in adhesion. However, the liquid composition (g1)
The amount of the caprolactone component extracted from the test piece obtained from was 9% by weight, the flicker elimination voltage was 80 mV, and the image sticking was “poor”.

Comparative Example 2 (A) 50 parts by weight of carbon black as a pigment and 15 parts by weight of barium sulfate, (B) 15 parts by weight of a polyethyleneimine-based dispersant (trade name: Solsperse24000) as a dispersant,
(C) (meth) acrylic acid as an alkali-soluble resin /
Monosuccinate [2- (meth) acryloyloxyethyl]
/ N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer (copolymerization weight ratio = 15/25 /
35/10/15, Mw = 30,000, Mn = 10,
000) 100 parts by weight, (D) 50 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer,
(E) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone as a photopolymerization initiator
1 and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a radiation-sensitive composition liquid composition (bk1).

Formation of Black Matrix The liquid composition (bk1) 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 heated at 90 ° C. Pre-bake for 10 minutes in a clean oven to obtain a film thickness of 5 μm
Was formed. Next, after the substrate was cooled to room temperature, the coating film was exposed to ultraviolet light having each wavelength of 365 nm, 405 nm and 436 nm at an exposure amount of 4,000 J / m ² through a photomask using a high-pressure mercury lamp. Thereafter, the substrate was immersed in a 0.04% by weight aqueous solution of potassium hydroxide at 23 ° 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 black matrix having a black pattern formed on the substrate.

[0084] When a black matrix obtained evaluation was observed using an optical microscope, and development residue on the substrate in the unexposed portion was not observed, and was also excellent in adhesion to the substrate of the black matrix. However, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (bk1) was 7% by weight,
Flicker erasing voltage is 60mV, burn-in is "bad"
Met.

[0085]

Example 1 (A) 80 parts by weight of CI Pigment Green 7 as a pigment and (B) a urethane-based dispersant (trade name: Disp.
erbyk-170) 12 parts by weight, (C) alkali-soluble resin (meth) acrylic acid / mono [2- (meth) acryloyloxyethyl] succinate / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer Combined (copolymerization weight ratio = 15/25/35/10/15, Mw = 3
0000, Mn = 10,000) 100 parts by weight,
(D) 50 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (E) 50 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator. The liquid composition (G1) of the radiation-sensitive composition was prepared by mixing the weight part and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent. A green striped pixel array was formed on a substrate in the same manner as in Comparative Example 1 except that the liquid composition (G1) for forming a pixel array was used.

[0086] When a pixel array obtained evaluation was observed using an optical microscope, also through hole 5μm angles are open, the developer left on the substrate in the unexposed portion was not observed, and the substrate of the pixel Was also excellent in adhesion. Moreover, the liquid composition (G1)
The amount of the caprolactone component extracted from the test piece obtained from was 3% by weight, the flicker elimination voltage was 20 mV, and the image sticking was “good”.

Example 2 (A) 80 parts by weight of CI Pigment Green 7 as a pigment, and (B) a urethane-based dispersant (trade name: Disp.
erbyk-170) 12 parts by weight, (C) methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer (copolymerization weight ratio = 15/25/35/10) as alkali-soluble resin
/ 15, Mw = 30,000, Mn = 10,000) 7
5 parts by weight, (D) 75 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (E) 2-benzyl-2-dimethylamino-1- as a photopolymerization initiator.
A liquid composition (G2) of a radiation-sensitive composition was prepared by mixing 50 parts by weight of (4-morpholinophenyl) butanone-1 and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent. A green striped pixel array was formed on a substrate in the same manner as in Comparative Example 1 except that the liquid composition (G2) for forming a pixel array was used.

[0088] When a pixel array obtained evaluation was observed using an optical microscope, also through hole 5μm angles are open, the developer left on the substrate in the unexposed portion was not observed, and the substrate of the pixel Was also excellent in adhesion. Moreover, the liquid composition (G2)
The extraction amount of the caprolactone component of the test piece obtained from was 1% by weight of the test piece, the flicker elimination voltage was 5 mV,
The burn-in was “excellent”.

Example 3 (A) 50 parts by weight of carbon black as a pigment,
(B) a urethane-based dispersant (trade name: Disperby)
k-165) 15 parts by weight, (C) methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer as an alkali-soluble resin (copolymerization weight ratio = 15/25/35/10/1)
5, Mw = 30,000, Mn = 10,000) 100
Parts by weight, (D) 50 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (E) 2-benzyl-2-dimethylamino-1- as a photopolymerization initiator.
A liquid composition (BK1) of a radiation-sensitive composition was prepared by mixing 50 parts by weight of (4-morpholinophenyl) butanone-1 and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent. Formation of Black Matrix A black matrix was formed on a substrate in the same manner as in Comparative Example 2 except that the liquid composition (BK1) was used.

[0090] When a black matrix obtained evaluation was observed using an optical microscope, and development residue on the substrate in the unexposed portion was not observed, and was also excellent in adhesion to the substrate of the black matrix. Moreover, the amount of the caprolactone component extracted from the test piece obtained from the liquid composition (BK1) was 2% by weight,
The flicker elimination voltage was 25 mV, and the burn-in was “good”.

Example 4 (A) 50 parts by weight of CI Pigment Black as a pigment,
(B) a urethane-based dispersant (trade name: Disperby)
k-170) 15 parts by weight, (C) methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer as an alkali-soluble resin (copolymerization weight ratio = 15/25/35/10/1)
5, Mw = 30,000, Mn = 10,000) 75 parts by weight, (C) 75 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (E) 2-benzyl-2 as a photopolymerization initiator. -Dimethylamino-1- (4
-Morpholinophenyl) butanone-1 by 50 parts by weight,
And 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (BK2) of the radiation-sensitive composition. Formation of Black Matrix A black matrix was formed on a substrate in the same manner as in Comparative Example 2 except that the liquid composition (BK2) was used.

[0092] When a black matrix obtained evaluation was observed using an optical microscope, and development residue on the substrate in the unexposed portion was not observed, and was also excellent in adhesion to the substrate of the black matrix. Moreover, the amount of the caprolactone component extracted from the test piece obtained from the liquid composition (BK2) was 2% by weight,
The flicker elimination voltage was 8 mV, and the burn-in was "excellent".

Example 5 (A) 80 parts by weight of CI Pigment Green 7 as a pigment, (B) 12 parts by weight of a polyethyleneimine-based dispersant (Solsperse 24000) as a dispersant, and (C) (meth) as an alkali-soluble resin Acrylic acid / mono [2- (meth) acryloyloxyethyl] succinate / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer (copolymerization weight ratio = 15/25/35/10 /
15, Mw = 30,000, Mn = 10,000) 60
Parts by weight, (D) 90 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (E) 2-benzyl-2-dimethylamino-1- as a photopolymerization initiator.
A liquid composition (BK3) of a radiation-sensitive composition was prepared by mixing 50 parts by weight of (4-morpholinophenyl) butanone-1 and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent. Formation of Black Matrix A black matrix was formed on a substrate in the same manner as in Comparative Example 2 except that the liquid composition (BK3) was used.

[0094] When a black matrix obtained evaluation was observed using an optical microscope, and development residue on the substrate in the unexposed portion was not observed, and was also excellent in adhesion to the substrate of the black matrix. Moreover, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (BK3) was 3% by weight,
The flicker elimination voltage was 24 mV, and the burn-in was “good”.

Example 6 (A) 50 parts by weight of carbon black as a pigment, (B)
Polyethyleneimine dispersant (trade name: Sols)
perse24000) 15 parts by weight, (C) methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer as an alkali-soluble resin (copolymerization weight ratio = 15/25/35/1)
0/15, Mw = 30,000, Mn = 10,000)
60 parts by weight, (D) 90 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (E) 2-benzyl-2-dimethylamino-1 as a photopolymerization initiator.
A liquid composition (BK4) of a radiation-sensitive composition was prepared by mixing 50 parts by weight of-(4-morpholinophenyl) butanone-1 and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent. Formation of Black Matrix A black matrix was formed on a substrate in the same manner as in Comparative Example 2 except that the liquid composition (BK4) was used.

[0096] When a black matrix obtained evaluation was observed using an optical microscope, and development residue on the substrate in the unexposed portion was not observed, and was also excellent in adhesion to the substrate of the black matrix. Moreover, the amount of the caprolactone component extracted from the test piece obtained from the liquid composition (BK4) was 2% by weight,
The flicker erasing voltage was 28 mV, and the burn-in was "good".

[0097]

The radiation-sensitive composition for a color liquid crystal display device of the present invention does not cause image sticking when the display panel is operated, and has a conductive property of 5 μm or less such as a through hole or a U-shaped depression. Can form a passage,
There is no development residue at the time of development, and the adhesiveness with a driving substrate on which a thin film transistor (TFT) is disposed or 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 quality, high definition color liquid crystal display device having a high aperture ratio.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 5/00 G02B 5/00 B 4J011 G02F 1/1335 505 G02F 1/1335 505 4J026 1/1368 G03F 7 / 004 505 4J027 G03F 7/004 505 7/027 502 7/027 502 C08F 299/02 // C08F 299/02 G02F 1/136 500 (72) Inventor Takeshi Watanabe 2-11-24 Tsukiji, Chuo-ku, Tokyo Jay F-term (reference) within SRL Co., Ltd. PA70 PA74 PA76 PA86 PB24 PB25 PB39 QA08 QA13 QA21 QA22 QA23 QA24 QA34 QA38 QA42 Q B05 QB14 QB16 QB20 QB24 QB25 RA03 RA04 RA05 RA10 RA11 RA12 SA14 SA15 SA16 SA19 SA20 SA78 SA82 SA83 TA03 TA06 TA07 TA08 UA01 UA03 UA04 UA06 VA01 WA01 4J026 AA17 AA43 AA45 BAA ABA ABA ABA ABA ABA ABA ABA ABA ABA ABA ABA ABA ABA ABA ABA ABA ABA A BA A BB02 DB26 DB28 DB29 DB30 DB36 GA07 4J027 AA04 AB10 AC03 AC04 AC06 AE01 AE07 AF05 BA16 BA20 BA23 BA24 BA26 BA27 BA28 CA02 CA03 CA34 CB10 CC04 CC05 CC06 CC08 CD10

Claims (2)

[Claims] 1. A radiation-sensitive color liquid crystal display device comprising (A) a pigment, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer and (E) a photopolymerization initiator. A thin film transistor (TFT) mode color liquid crystal, characterized in that an extraction amount of a caprolactone component by acetonitrile of a colored layer formed from the composition is 5% by weight or less of the colored layer. A radiation-sensitive composition for a color liquid crystal display device used for forming a colored layer on a driving substrate of a display device. 2. The color liquid crystal display device according to claim 1, wherein a color layer is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device directly or via a passivation film. A color liquid crystal display device formed from a radiation-sensitive composition for a liquid crystal display device.