JP5114979B2 - Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new radiation-sensitive composition for colored layer formation which exhibits excellent developability even when a high colorant concentration, generates neither development residue nor scum on a pattern edge in development, excels in linearity of a pattern, and gives ultrafine pixels and a black matrix. <P>SOLUTION: The radiation-sensitive composition for colored layer formation comprises (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator, wherein the alkali-soluble resin (B) comprises a polymer having a carboxyl group at a terminal of a polymer chain. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display element, and more particularly, in a color filter used for a transmissive or reflective color liquid crystal display device, a color imaging tube element, and the like. The present invention relates to a radiation-sensitive composition used for forming a colored layer, a color filter having a colored layer formed using the radiation-sensitive composition, and a color liquid crystal display device including the color filter.

Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, A method of obtaining pixels of each color by irradiating a dry coating film with a desired pattern shape (hereinafter referred to as “exposure”) and developing it is known (see, for example, Patent Document 1 and Patent Document 2). ing.
In recent years, color liquid crystal display elements for monitors and televisions have been desired to have brighter screens with better color reproducibility. In addition to improving the brightness of the backlight, the colorant contained in the colored radiation-sensitive composition In particular, it has become necessary to increase the pigment content (see, for example, Non-Patent Document 1).
However, as the content of the colorant contained in the colored radiation-sensitive composition increases, undissolved matter (that is, development residue) and background stains are likely to occur on the substrate other than the pattern formation region, and formation is also caused. There is a problem that the linearity of the formed pattern is impaired, and it tends to be a rough shape. Furthermore, the screens of monitors and televisions are becoming higher definition, and the number of pixels per unit area on the screen tends to increase. Therefore, for both pixel formation and black matrix formation, more colored radiation-sensitive compositions are used. It is also demanded that a fine pattern can be formed.

JP-A-2-144502 JP-A-3-53201 Published by Kei Murakami, “New Development of LCD Front and Backlight”, 1st Edition, Toray Research Center, Inc., September 2002

  The subject of the present invention is a radiation-sensitive composition for forming a colored layer, which exhibits excellent developability even when the concentration of the colorant is high, and more specifically, development residue and scum of pattern edges during development, etc. It is an object to provide a novel radiation-sensitive composition for forming a colored layer, which has excellent pattern linearity and gives high fine pixels and a black matrix.

（式中、Ｒ¹ は炭素数１〜１２の直鎖状、分岐状もしくは環状のアルキル基または炭素数６〜１２のアリール基を示す。）

（式中、各Ｒ² は相互に独立に水素原子、ハロゲン原子、ヒドロキシル基、ヒドロキシメチル基またはカルボキシル基を示す。）

（式中、各Ｒ ³ は相互に独立にメチレン基、炭素数２〜１２のアルキレン基または炭素数６〜１２のアリーレン基を示す。）
本発明でいう「重合体鎖の末端」は、重合体鎖の末端近傍を含む。
また、本発明でいう「着色層」は、カラーフィルタに用いられる画素および／またはブラックマトリックスからなる層を意味する。 The present invention, first,
In the radiation-sensitive composition for forming a colored layer, comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. The resin has a structural unit represented by the following formula (1) and / or a structural unit represented by the following formula (2), and a radical polymerization initiator represented by the following formula (3) is an essential component. Including an addition polymerization polymer having a carboxyl group at least at one end of a polymer chain , which is produced by radical polymerization in the presence of a radical polymerization initiator having one or more carboxyl groups in the molecule. It consists of the radiation sensitive composition for colored layer formation characterized by the above-mentioned.

(In the formula, R ¹ represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.)

(In the formula, each R ² independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group.)

(In formula, each R < ³ > shows a methylene group, a C2-C12 alkylene group, or a C6-C12 arylene group mutually independently.)
The “end of the polymer chain” in the present invention includes the vicinity of the end of the polymer chain.
The “colored layer” in the present invention means a layer composed of pixels and / or a black matrix used for a color filter.

The present invention secondly,
The color filter which has a colored layer formed using the said radiation sensitive composition for colored layer formation.

Third, the present invention
A color liquid crystal display device comprising the color filter;

Hereinafter, the present invention will be described in detail.
Radiation-sensitive composition for forming colored layer- (A) Colorant-
The colorant in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter, and may be any of a pigment, a dye, or a natural pigment.
Since the color filter is required to have high-definition color development and heat resistance, the colorant in the present invention is preferably a colorant having high color developability and high heat resistance, in particular, a colorant having high heat decomposition resistance. Organic pigments or inorganic pigments are used, and organic pigments and carbon black are particularly preferably used.
Examples of the organic pigment include a color index (CI; The Society of Dyers).
and Colorists (published by and Colorists)), specifically, compounds 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 71, 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 CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment ...... DOO Yellow 155, C.I Pigment Yellow 156, C.I Pigment Yellow 166, C.I Pigment Yellow 168, C.I Pigment Yellow 175, C.I Pigment Yellow 180, C.I Pigment Yellow 185;

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, 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, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38;

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 10, 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, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI CI Pigment Red 50: 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 pigmentless 97,

CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, 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 122, 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 170, 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 178, 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 202, 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 220, 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, C.I. Pigment Red 265;

CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60;
CI Pigment Green 7, CI Pigment Green 36;
CI Pigment Brown 23, CI Pigment Brown 25;
CI Pigment Black 1, CI Pigment Black 7.
These organic pigments can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

  Examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean curd (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

  In the present invention, the organic pigment and the inorganic pigment can be used alone or in combination of two or more, and the organic pigment and the inorganic pigment can be used together. Preferably, one or more organic pigments are used, and when forming the black matrix, two or more organic pigments and / or carbon black are preferably used.

In the present invention, each of the pigments can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the pigment particle surface include the polymers described in Patent Document 3 and the like, and various commercially available polymers or oligomers for dispersing pigments.
JP-A-8-259876

Moreover, in this invention, a coloring agent can be used with a dispersing agent depending on necessity. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl. Polyoxyethylene alkyl phenyl ethers such as phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; polyethyleneimines In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and F-Top (manufactured by Tochem Products). Megafuck (Dainippon Ink and Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass Co., Ltd.), Dispersbyk (Bicchemy Japan), Solsparse (Seneca Co., Ltd.).
These surfactants can be used alone or in admixture of two or more.
The usage-amount of surfactant is 50 parts weight or less normally with respect to 100 weight part of coloring agents, Preferably it is 0-30 weight part.

  In the present invention, the radiation-sensitive composition can be prepared by an appropriate method. When a pigment is used as a colorant, the pigment is used in a solvent in the presence of a dispersant, as will be described later (B). Along with an alkali-soluble resin, for example, a bead mill, a roll mill or the like may be mixed and dispersed while being pulverized to obtain a pigment dispersion, which may be prepared by mixing with components (B) to (D) described later. preferable.

The amount of the dispersant used in preparing the pigment dispersion is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, particularly 100 parts by weight of the pigment. Preferably it is 10-50 weight part. In this case, when there is too much usage amount of a dispersing agent, there exists a possibility that developability etc. may be impaired.
Moreover, as a solvent used when preparing a pigment dispersion liquid, the thing similar to the solvent illustrated about the liquid composition of the radiation sensitive composition mentioned later can be mentioned, for example.
The amount of the solvent used in preparing the pigment dispersion is usually 200 to 1,200 parts by weight, preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment.

When preparing a pigment dispersion using a bead mill, for example, glass beads or titania beads having a diameter of about 0.5 to 10 mm are used, and a pigment mixture composed of a pigment, a solvent, a dispersant, and the like is used. Preferably, it can be carried out by mixing and dispersing while cooling with cooling water or the like.
In this case, the filling rate of the beads is usually 50 to 80% of the mill capacity, and the injection amount of the pigment mixed solution is usually about 20 to 50% of the mill capacity. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.
Moreover, when preparing using a roll mill, it can carry out by processing, for example, using a 3 roll mill, a 2 roll mill, etc., preferably cooling a pigment liquid mixture with cooling water etc.
In this case, the roll interval is preferably 10 μm or less, and the shearing force is usually about 10 ⁸ dyn / sec. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.

-(B) Alkali-soluble resin-
The alkali-soluble resin used in the present invention is a structural unit represented by the formula (1) (hereinafter referred to as “structural unit (1)”) and / or a structural unit represented by the formula (2) ( Hereinafter, the radical polymerization initiator (hereinafter referred to as “radical polymerization initiator (3)”) represented by the formula (3) having the “structural unit (2)” is an essential component. At least one polymer chain produced by radical polymerization in the presence of a radical polymerization initiator having one or more carboxyl groups in the molecule (hereinafter referred to as “carboxyl group-containing radical polymerization initiator”). A development process in which an addition polymerization polymer having a carboxyl group at the end (hereinafter referred to as “polymer (B1)”) is used, and (A) acts as a binder for the colorant and forms a colored layer. In the process A component having a solubility in an alkali developing solution need.

In the polymer (B1), for example, in the presence of a carboxyl group-containing radical polymerization initiator in a good solvent inert to the polymerizable unsaturated compound, the reaction temperature is usually 0 to 150 ° C., preferably 50 to 120. It can manufacture by carrying out radical polymerization as ° C.

In the radical polymerization, when the carboxyl group-containing radical polymerization initiator has a carboxyl group only on one side of the binding site that decomposes during polymerization to generate radicals, usually at least one terminal of the polymer (B1) or When a carboxyl group is introduced in the vicinity of at least one terminal and has carboxyl groups on both sides of the binding site, the carboxyl group is usually introduced in all terminals or in the vicinity of all terminals of the polymer (B1) .

Specific examples of the radical polymerization initiator (3) include 4,4′-azobis (4-cyanopropionic acid), 4,4′-azobis (4-cyanobutyric acid), 4,4′-azobis (4-cyanovalerin). Acid), 4,4′-azobis (4-cyanoethylbenzoic acid), 4,4′-azobis (4-cyanoethylcyclohexanecarboxylic acid), and the like.
Of these radical polymerization initiators (3), 4,4′-azobis (4-cyanovaleric acid) is particularly preferable.
In the said radical polymerization, a carboxyl group-containing radical polymerization initiator can be used individually or in mixture of 2 or more types.

Moreover, in this invention, another radical polymerization initiator can also be used together with a carboxyl group-containing radical polymerization initiator.
Examples of the other radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy). -2,4-dimethylvaleronitrile) and the like.
These other radical polymerization initiators can be used alone or in admixture of two or more.

In the present invention, when the carboxyl group-containing radical polymerization initiator is used in combination with another radical polymerization initiator, the proportion of the carboxyl group-containing radical polymerization initiator used is preferably 10 to 100% by weight, particularly preferably 30 to 100%. % By weight. In this case, if the proportion of the carboxyl group-containing radical polymerization initiator used is too small, the content of the polymer (B1) in the resulting polymer will be low, and the intended effect of the present invention may be impaired.

Moreover, as a solvent used for the radical polymerization, for example,
Alcohols such as methanol, ethanol, n-propanol, i-propanol;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate;
Ethylene glycol monoalkyl ether propionates such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate ;
Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Dipropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate;
Propylene glycol monoalkyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, propylene glycol monoalkyl ether propionate such as propylene glycol mono-n-butyl ether propionate ;

Other ethers such as tetrahydrofuran and dioxane;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;
Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropion N-propyl acid, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxypropionic acid n-butyl, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, 3-methoxy N-propyl propionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, 3-n -Methyl propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, 3-n- Alkyl alkoxypropionates such as ethyl butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate,

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, 4-methoxybutyl acetate, 2-methoxybutyl acetate, acetic acid 3 -Methoxybutyl, 3-ethoxybutyl acetate, 3-proxybutyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, Ethoxy methoxyacetate, methoxyacetic acid -Propyl, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyloxyacetate n-propyl, n -Other esters such as n-butyl propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-butoxyacetate, n-butyloxybutoxyacetate, and the like.

Of these solvents, ketones and propylene glycol monoalkyl ether acetates are preferable, and cyclohexanone, propylene glycol monoethyl ether, and the like are particularly preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Furthermore, the polymer (B1) can also be purified through a reprecipitation method using two or more organic solvents having different polarities after radical polymerization of the polymerizable unsaturated compound. That is, a good solvent solution of a polymer obtained by radical polymerization, or a solution obtained by separating and recovering a polymer from a solvent after radical polymerization and then re-dissolving in another same or different good solvent is filtered or centrifuged as necessary. After removing insoluble impurities by separation or the like, the mixture is poured into a large amount (usually 5 to 10 times the volume of the polymer solution) of a precipitating agent (poor solvent) to purify the polymer by reprecipitation. At that time, out of the impurities remaining in the polymer solution, impurities soluble in the precipitating agent remain in the liquid phase and are separated from the purified polymer (B1) .
Examples of the good solvent / precipitant combination used in this reprecipitation method include cyclohexanone / n-hexane, propylene glycol monoethyl ether / n-hexane, cyclohexanone / n-heptane, propylene glycol monoethyl ether / n- And heptane.

In the formula (1), examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. Group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl Group, n-dodecyl group, cyclopentyl group, cyclohexyl group and the like.

The aryl group having 6 to 12 carbon atoms of R ^1, for example, a phenyl group, o- tolyl group, m- tolyl group, p- tolyl group, a 1-naphthyl group, there may be mentioned 2-naphthyl group it can.

In the formula (1), R ¹ is preferably a cyclohexyl group, a phenyl group or the like, and particularly preferably a phenyl group.

In the formula (2), examples of the halogen atom for R ² include a fluorine atom, a chlorine atom, and a bromine atom.
In the formula (2), R ² is preferably a hydrogen atom, a chlorine atom or the like, and particularly preferably a hydrogen atom.

  The structural unit (1) is a structural unit in which an unsaturated compound represented by the following formula (4) (hereinafter referred to as “unsaturated compound (4)”) is polymerized, and the structural unit (2) is represented by the following formula: This is a structural unit in which the unsaturated compound represented by (5) (hereinafter referred to as “unsaturated compound (5)”) is polymerized.

Specific examples of the unsaturated compound (4) include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, Examples thereof include Nn-hexylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-1-naphthylmaleimide and the like.
Of these unsaturated compounds (4), N-cyclohexylmaleimide, N-phenylmaleimide and the like are preferable, and N-phenylmaleimide is particularly preferable.
In a polymer (B1), an unsaturated compound (4) can be used individually or in mixture of 2 or more types.

Specific examples of the unsaturated compound (5) include acenaphthylene, 5-chloroacenaphthylene, 5-hydroxyacenaphthylene, 5-hydroxymethylacenaphthylene, 5-carboxyacenaphthylene and the like.
Of these unsaturated compounds (5), acenaphthylene, 5-chloroacenaphthylene and the like are preferable, and acenaphthylene is particularly preferable.
In a polymer (B1), an unsaturated compound (5) can be used individually or in mixture of 2 or more types.

  In addition, the polymer (B1) is a polymerizable unsaturated compound having at least one or at least one acidic functional group such as a carboxyl group, a carboxylic acid anhydride group, and a phenolic hydroxyl group in the molecule as another structural unit. (Hereinafter referred to as “acidic unsaturated compound”) and other polymerizable unsaturated compounds (hereinafter referred to as “other unsaturated compounds”) may have a polymerized structural unit.

As an acidic unsaturated compound, for example,
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof;
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate;
o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol Unsaturated phenols such as
2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, etc. Of unsaturated naphthols.
Succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are trade names of light ester HOA-MS and light ester HOA-MPE (above, manufactured by Kyoeisha Chemical Co., Ltd.), respectively. Is commercially available.

  Of these acidic unsaturated compounds, (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylphenol, and the like are particularly preferable. , (Meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate and the like are preferable.

Moreover, as another unsaturated compound, for example,
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
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, diethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, propylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meta) ) Unsaturated carboxylic acid esters such as acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
In the polymer (B1), the acidic unsaturated compound and other unsaturated compounds can be used alone or in combination of two or more, and the acidic unsaturated compound and other unsaturated compounds are used in combination. can do.

In the present invention, as a preferred polymer (B1), more specifically, for example,
(I) at least one selected from the group consisting of N-cyclohexylmaleimide, N-phenylmaleimide, acenaphthylene and 5-chloroacenaphthylene, and (ii) (meth) acrylic acid, succinic acid mono [2- (meth) acrylic At least one selected from the group of leuoxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate, and (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate , A copolymer with at least one selected from the group of benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer,

More preferable polymer (B1) is more specifically, for example,
(I) N-phenylmaleimide, (ii) (meth) acrylic acid, (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate , A copolymer (B1-1) with at least one selected from the group of phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer;
(I) N-phenylmaleimide, (ii) ω-carboxypolycaprolactone mono (meth) acrylate, (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, A copolymer (B1-2) with at least one selected from the group of benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer;
(I) N-phenylmaleimide, (ii) a mixture of (meth) acrylic acid and ω-carboxypolycaprolactone mono (meth) acrylate, (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meta ) Acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer. Polymer (B1-3);

(I) acenaphthylene, (ii) (meth) acrylic acid, (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl ( A copolymer (B1-4) with at least one selected from the group of (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer;
(I) acenaphthylene, (ii) ω-carboxypolycaprolactone mono (meth) acrylate, (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meta ) Copolymer (B1-5) with at least one selected from the group of acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer;
(I) acenaphthylene, (ii) a mixture of (meth) acrylic acid and ω-carboxypolycaprolactone mono (meth) acrylate, (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Copolymer with at least one selected from the group consisting of allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer ( B1-6);

(I) a mixture of N-phenylmaleimide and acenaphthylene, (ii) (meth) acrylic acid, (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, A copolymer (B1-7) with at least one selected from the group consisting of benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer;
(I) a mixture of N-phenylmaleimide and acenaphthylene, (ii) ω-carboxypolycaprolactone mono (meth) acrylate, (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl Copolymer with at least one selected from the group of (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer (B1 -8);
(I) a mixture of N-phenylmaleimide and acenaphthylene, (ii) a mixture of acrylic acid and ω-carboxypolycaprolactone mono (meth) acrylate, and (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl At least one selected from the group of (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer; Copolymer (B1-9)
Etc.

  Of these copolymers, the copolymer (B1-1), the copolymer (B1-4), the copolymer (B1-7) and the like are particularly preferable.

In the copolymer (B1), the total content of the unsaturated compound (4) and the unsaturated compound (5) is preferably 1 to 70% by weight, particularly preferably 10 to 40% by weight, and the acidic unsaturated compound The content of is preferably 1 to 40% by weight, particularly preferably 5 to 30% by weight, and the content of other unsaturated compounds is preferably 1 to 90% by weight, particularly preferably 5 to 70% by weight. It is.
In this invention, the radiation sensitive composition for colored layer formation which shows the outstanding developability can be obtained by making content rate of each unsaturated compound in a polymer (B1) into the said range.

  Furthermore, in the present invention, for example, in the case of a polymer (B1) obtained by (co) polymerizing a polymerizable unsaturated compound having a hydroxyl group such as 5-hydroxyacenaphthylene and 2-hydroxyethyl (meth) acrylate, For example, a polymerizable unsaturated bond can be introduced into the side chain of the polymer (B1) by reacting an isocyanate compound having a polymerizable unsaturated group such as 2- (meth) acryloyloxyethyl isocyanate.

The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the polymer (B1) is usually 1,000 to 45,000, preferably 3,000 to 20,000. In this case, if the Mw of the polymer (B1) is too low, the remaining film ratio, pattern shape, heat resistance, electrical properties, etc. of the resulting coating may be impaired, while if too high, the resolution and pattern shape are impaired. In addition, there is a risk that dry foreign matter is likely to occur during application by the slit nozzle method.
The number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the polymer (B1 ) is usually 1,000 to 45,000. Preferably it is 3,000-20,000.
Moreover, the ratio (Mw / Mn ) of Mw and Mn of the polymer (B1) is usually 1.0 to 5.0, preferably 1.0 to 3.0.
In this invention, a polymer (B1) can be used individually or in mixture of 2 or more types.

In the present invention, as an alkali-soluble resin component, together with the polymer (B1) , an alkali developer used in the development processing step when acting as a binder for the colorant (A) and forming a colored layer It is possible to use other polymers that are soluble in
Examples of the other polymer include a copolymer of the acidic unsaturated compound with the unsaturated compound (4) and other unsaturated compounds.
In other polymers, the acidic unsaturated compound, the unsaturated compound (4) and the other unsaturated compound can be used alone or in admixture of two or more, and the unsaturated compound (4) and It can be used by mixing with other unsaturated compounds.

In this invention, the total usage-amount of alkali-soluble resin is 10-1,000 weight part normally with respect to 100 weight part of (A) coloring agents, Preferably it is 20-500 weight part. In this case, if the total amount of the alkali-soluble resin used is too small, for example, the alkali developability may be lowered, or a development residue or background stains may be generated on the unexposed substrate or the light shielding layer. If it is too high, the colorant concentration is relatively lowered, and it may be difficult to achieve the target color density as a thin film.
The proportion of the polymer when used in combination with the polymer (B1) and another polymer (B1), based on the total of the carboxyl terminated polymers with other polymers, usually 30 wt% or more It is preferably 50% by weight or more. In this case, if the use ratio of the polymer (B1) is too small, the intended effect of the present invention may be impaired.

-(C) polyfunctional monomer-
The polyfunctional monomer in this invention consists of a monomer which has a 2 or more polymerizable unsaturated bond.
As the multifunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene, both terminal hydroxypolycaprolactone,
And tris [2- (meth) acryloyloxyethyl] phosphate.

  Of these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified products, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate,

Compound represented by the following formula (6), compound represented by the following formula (7)

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high strength of the colored layer, excellent surface smoothness of the colored layer, and on the unexposed substrate and the light shielding layer. It is preferable in that development residue, background stains and the like are hardly generated on the top.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of (B) alkali-soluble resin, Preferably it is 20-300 weight part. In this case, if the amount of the polyfunctional monomer used is too small, the strength and surface smoothness of the colored layer tend to decrease. On the other hand, if the amount used is too large, for example, alkali developability decreases or unexposed areas. There is a tendency that development residues, background stains, and the like are likely to occur on the substrate or the light shielding layer.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include the unsaturated compound (4), acidic unsaturated compounds and compounds similar to other unsaturated compounds, N- (meth) acryloylmorpholine, N-vinylpyrrolidone. N-vinyl-ε-caprolactam and commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
These monofunctional monomers can be used alone or in admixture of two or more.

  The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, if the usage ratio of the monofunctional monomer is too large, the strength and surface smoothness of the resulting colored layer may be insufficient. The total use amount of the polyfunctional monomer and the monofunctional monomer in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the (B) alkali-soluble resin. Part. In this case, if the total amount used is too small, the strength and surface smoothness of the colored layer tend to be reduced. On the other hand, if the total amount is too large, for example, alkali developability is lowered, the substrate on the unexposed area or light shielding is performed. There is a tendency that development residues, background stains, and the like are likely to occur on the layer.

-(D) Photopolymerization initiator-
The photopolymerization initiator in the present invention is the above-mentioned (C) polyfunctional monomer and a monofunctional monomer used in some cases by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a component that generates an active radical or an active acid, or both an active radical and an active acid that can initiate polymerization of the body.
Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. , Polynuclear quinone compounds, xanthone compounds, diazo compounds, imide sulfonate compounds, and the like.

  In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, an acetophenone compound, a biimidazole compound, a triazine compound, At least one selected from the group of O-acyloxime compounds is preferable, and acetophenone compounds, O-acyloxime compounds, and the like are particularly preferable.

  In this invention, the general usage-amount of a photoinitiator is 0.01-120 weight normally with respect to a total of 100 weight part of (C) polyfunctional monomer and a monofunctional monomer. Parts, preferably 1 to 100 parts by weight. In this case, if the amount of the photopolymerization initiator used is too small, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement, while too much. Then, the formed colored layer tends to be easily detached from the substrate during development.

Among 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- Examples include 1,2-diphenylethane-1-one and 1,2-octanedione.
Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Butan-1-one, 1,2-octanedione and the like are preferable.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, when the acetophenone compound is used as the photopolymerization initiator, the amount used is usually 0 with respect to 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. 0.01 to 80 parts by weight, preferably 1 to 70 parts by weight, and more preferably 1 to 60 parts by weight. In this case, if the amount of the acetophenone-based compound used is too small, curing due to exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. The formed colored layer tends to easily fall off from 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′-bi Imidazole, 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'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2, 2'-bis (2-bromophenyl)- , 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′-tetraphenyl-1,2′-biimidazole and the like are preferable, and in particular, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole is preferred.
These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, and have high sensitivity. Since no curing reaction occurs in the exposed area, the coated film after exposure is clearly divided into a cured area that is insoluble in the developer and an uncured area that has high solubility in the developer, Thereby, a high-definition color filter in which a colored layer pattern without an undercut is arranged according to a predetermined arrangement can be formed.
The biimidazole compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used in the case of using a biimidazole compound as a photopolymerization initiator is usually (C) with respect to a total of 100 parts by weight of the polyfunctional monomer and the monofunctional monomer, 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 compound used is too small, curing due to exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement, while too much. When developing, there is a tendency that the formed colored layer is easily detached from the substrate and the surface of the colored layer is likely to come off.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor described below in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like 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, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ Mercaptan-based hydrogen donor ").
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “ Amine-based hydrogen donor ").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, 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 are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

In addition, the amine hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. A ring may or may not be formed.
In addition, in the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine-based hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of radical generators other than biimidazole compounds.

In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed colored layer does not easily fall off from the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of the combination of a mercaptan hydrogen donor and an amine 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, and the like, and more preferred combinations 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / , 4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 1 to 1: 4, preferably 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 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the hydrogen donor used is too small, the effect of improving the sensitivity tends to be lowered. On the other hand, if the amount is too large, the formed colored layer tends to be detached from the substrate during development.

  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 (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

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

  In the present invention, the amount of triazine compound used as the photopolymerization initiator is preferably 0 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the triazine compound used is too small, curing due to exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement, while if too large, The formed colored layer tends to easily fall off from the substrate during development.

  Specific examples of the O-acyloxime compound include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime), 1- [4- (phenylthio). Phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H-carbazole -3-yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetate) Ruokishimu) ethanone 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyl Ruben benzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) benzoyl} -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

Among these O-acyloxime compounds, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like are preferable.
The O-acyloxime compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used in the case of using an O-acyloxime compound as a photopolymerization initiator is based on 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. Preferably it is 0.01-80 weight part, More preferably, it is 1-70 weight part, Most preferably, it is 1-60 weight part. In this case, if the amount of the O-acyloxime compound used is too small, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. When the amount is too large, the formed colored layer tends to be easily detached from the substrate during development.

-Additives-
The radiation-sensitive composition for forming a colored layer of the present invention can contain various additives as necessary.
Examples of the additive include an organic acid or an organic amino compound (provided that the solubility of the radiation-sensitive composition in an alkaline developer is further improved, and further suppresses the generation of development residues after development). The hydrogen donor is excluded).

The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.
Examples of the aliphatic carboxylic acid include
Monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
And 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 the phenyl group, and a carboxylic acid in which the carboxyl group is bonded to the 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, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples thereof include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

Among these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in a solvent described later, development residue on the unexposed substrate or light-shielding layer, and prevention of background contamination. Dicarboxylic acids are preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are particularly preferred. As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferable, and phthalic acid is particularly preferable.
The organic acids can be used alone or in admixture of two or more.
The amount of the organic acid used is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. In this case, when there is too much usage-amount of organic acid, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

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, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4- Mono (cyclo) alkylamines such as 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 Di (cyclo) alkylamines such as t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri-i-propylamine, tri- n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexyl Tri (cyclo) alkylamines such as amine 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- Mono (cyclo) alkanolamines such as 1-cyclohexanol;

Diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, di-n-hexanolamine, di (4-cyclo Di (cyclo) alkanolamines such as hexanol) amine;
Triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4 -Tri (cyclo) alkanolamines such as 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-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol Amino (cyclo) alkanediols such as 2-diethylamino-1,3-propanediol;
1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4- Amino group-containing cycloalkanemethanols such as diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Examples thereof include aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Examples of the phenyl group-containing amine include compounds in which an amino group is directly bonded to a phenyl group, and compounds in which an amino group is bonded to a phenyl group via a carbon chain.
As the phenyl group-containing amine, for example,
Aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4-n-butylaniline, 4-t-butylaniline, Aromatic amines such as 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, 4-methyl-N, N-dimethylaniline;
Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol;
Examples include aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, mono (cyclo) alkanolamines are used as aliphatic amines from the viewpoints of solubility in a solvent described later, prevention of development residue and background contamination on the unexposed substrate or light shielding layer, and the like. And 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. Moreover, as a phenyl group containing amine, aminophenols are preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. are especially preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The amount of the organic amino compound used is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. In this case, when there is too much usage-amount of an organic amino compound, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Furthermore, as an additive other than the organic acid and the organic amino compound, for example,
Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Examples thereof include thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

Solvent The radiation-sensitive composition for forming a colored layer according to the present invention contains the components (A) to (D) as essential components, and contains the additive components as necessary. Prepared as a composition.
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

As such a solvent, for example,
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, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as 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, propylene glycol monoethyl ether acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate , N-propyl pyruvate, methyl acetoacetate, acetoacetate Le, other esters such as ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl from the viewpoint of pigment dispersibility, solubility, coatability, etc. Ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, butyric acid - propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
These high-boiling solvents can be used alone or in admixture of two or more.
The amount of the solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the composition is usually from the viewpoint of applicability, stability and the like of the obtained radiation-sensitive composition. An amount of 5 to 50% by weight, preferably 10 to 40% by weight, is desirable.

Color filter The color filter of this invention has a colored layer formed using the radiation-sensitive composition for colored layer formation of this invention.
The method for forming the color filter of the present invention will be described below.
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming pixels, and a liquid composition of a radiation sensitive composition in which, for example, a red pigment is dispersed on the substrate. After applying the material, pre-baking is performed to evaporate the solvent and form a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a red pixel pattern. A pixel array arranged in an array is formed.
Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the liquid composition is coated, pre-baked, exposed, developed, and post-baked in the same manner as described above. By sequentially forming the pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.
The black matrix can be formed in the same manner as in the case of forming the pixel, for example, using the radiation-sensitive composition for forming a colored layer of the present invention in which a black pigment is dispersed.

Examples of the substrate used when forming the pixel and / or the black matrix include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When applying a liquid composition of a radiation sensitive composition to a substrate, an appropriate application such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, etc. Although a method can be employed, a spin coating method and a slit die coating method are particularly preferable.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of radiation is preferably 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [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 alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

  The color filter of the present invention thus obtained is extremely useful for, for example, a transmissive or reflective color liquid crystal display element, a color imaging tube element, a color sensor, and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
Further, as one embodiment of the color liquid crystal display element of the present invention, a pixel and / or a black matrix is formed on a thin film transistor substrate array as described above using the radiation-sensitive composition for forming a colored layer of the present invention. By forming a color liquid crystal display panel having particularly excellent characteristics can be produced.

The radiation-sensitive composition for forming a colored layer of the present invention uses an alkali-soluble resin containing the polymer (B1), so that even when the pigment is contained at a high concentration, the unexposed portion on the substrate and the light-shielding layer at the time of development. There is no development residue or background stain on the top, no scum is generated at the edge of the pixel pattern and the black matrix pattern, and the resolution is high and a high-definition pixel pattern and black matrix pattern can be formed. The pixels and the black matrix formed using the radiation-sensitive composition for forming a colored layer of the present invention are excellent in linearity and adhesiveness to the substrate.
Therefore, the radiation-sensitive composition for forming a colored layer of the present invention can be used very suitably for the production of various color filters including color filters for color liquid crystal display elements in the electronic industry.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Mw and Mn of the resin obtained in each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (manufactured by Showa Denko KK).
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 were used in combination.
Elution solvent: tetrahydrofuran containing 0.5% by weight of phosphoric acid.

Synthesis of polymer (B1) Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 4,4′-azobis (4-cyanovaleric acid) and 200 parts by weight of cyclohexanone, followed by 12.5 parts by weight of methacrylic acid, 25 parts by weight of N-phenylmaleimide, Charge 37.5 parts by weight of benzyl methacrylate, 15 parts by weight of styrene, 10 parts by weight of glycerol monomethacrylate, and 5 parts by weight of α-methylstyrene dimer which is a chain transfer agent as a molecular weight control agent. However, the temperature of the reaction solution was raised to 80 ° C., and polymerization was performed for 3 hours while maintaining this temperature. Thereafter, 0.5 part by weight of 4,4′-azobis (4-cyanovaleric acid) was added, and after further polymerizing for 1 hour, the temperature was raised to 100 ° C. and the polymerization was continued for 1 hour, whereby a polymer was obtained. (B1) A solution (solid content concentration = 33.0 wt%) was obtained. The obtained polymer (B1) was Mw = 10,000, (Mw / Mn) = 2.3, and was a polymer having carboxyl groups at both ends of the polymer chain. This polymer (B1) is referred to as “resin (B-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 4,4′-azobis (4-cyanovaleric acid) and 200 parts by weight of cyclohexanone, followed by 12.5 parts by weight of methacrylic acid, 52.5 parts by weight of benzyl methacrylate, Charge 25 parts by weight of styrene, 10 parts by weight of glycerol monomethacrylate, and 5 parts by weight of α-methylstyrene dimer. After purging with nitrogen, raise the temperature of the reaction solution to 80 ° C. with gentle stirring and maintain this temperature. And polymerized for 3 hours. Thereafter, 0.5 part by weight of 4,4′-azobis (4-cyanovaleric acid) was added, and after further polymerizing for 1 hour, the temperature was raised to 100 ° C. and the polymerization was continued for 1 hour, whereby a polymer was obtained. (B1) A solution (solid content concentration = 33.0 wt%) was obtained. The obtained polymer (B1) was Mw = 10,000, (Mw / Mn) = 2.3, and was a polymer having carboxyl groups at both ends of the polymer chain. This polymer (B1) is referred to as “resin (B-2)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 25 parts by weight of N-phenylmaleimide. , 35 parts by weight of benzyl methacrylate, 15 parts by weight of styrene, 10 parts by weight of glycerol monomethacrylate, and 5 parts by weight of α-methylstyrene dimer were charged, and the reaction solution was raised to 80 ° C. while gently stirring. The mixture was heated and polymerized for 3 hours while maintaining this temperature. Thereafter, 0.5 part by weight of 2,2′-azobisisobutyronitrile was added, and after further polymerizing for 1 hour, the temperature was raised to 100 ° C. and polymerization was continued for 1 hour, whereby a resin solution ( Solid content concentration = 33.0 wt%) was obtained. The obtained resin was Mw = 10,000 and (Mw / Mn) = 2.2. This resin is referred to as “resin (β-1)”.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 4,4′-azobis (4-cyanovaleric acid) and 200 parts by weight of propylene glycol monoethyl ether, followed by 12.5 parts by weight of methacrylic acid and 30 parts by weight of acenaphthylene. , 42.5 parts by weight of benzyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate, 5 parts by weight of ω-carboxypolycaprolactone monoacrylate, and 6 parts by weight of α-methylstyrene dimer were charged with nitrogen, and then gently stirred. However, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, 0.5 part by weight of 4,4′-azobis (4-cyanovaleric acid) was added, and after further polymerizing for 1 hour, the temperature was raised to 100 ° C. and the polymerization was continued for 1 hour, whereby a polymer was obtained. (B1) A solution (solid content concentration = 33.0 wt%) was obtained. The obtained polymer (B1) was Mw = 9,000, (Mw / Mn) = 2.3, and was a polymer having carboxyl groups at both ends of the polymer chain. This resin is referred to as “resin (B-3)”.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid, 30 parts by weight of acenaphthylene, and benzyl methacrylate. 40 parts by weight, 10 parts by weight of 2-hydroxyethyl methacrylate, 5 parts by weight of ω-carboxypolycaprolactone monoacrylate, and 6 parts by weight of α-methylstyrene dimer were charged with nitrogen, and then the reaction solution was stirred gently. Was heated to 80 ° C., and this temperature was maintained for polymerization for 3 hours. Thereafter, 0.5 part by weight of 2,2′-azobisisobutyronitrile was added, and after further polymerizing for 1 hour, the temperature was raised to 100 ° C. and polymerization was continued for 1 hour, whereby a resin solution ( Solid content concentration = 33.0 wt%) was obtained. The obtained resin was Mw = 9,000 and (Mw / Mn) = 2.2. This resin is referred to as “resin (β-2)”.

Example 1
Preparation of liquid composition (A) CI Pigment Red 254 / CI Pigment Red 177 = 80/20 (weight ratio) 15 parts by weight of a mixture as a colorant, Disperbyk-2001 4 parts by weight (in terms of solid content) as a dispersant, B) 6 parts by weight of methacrylic acid / N-phenylmaleimide / styrene / benzyl methacrylate copolymer (copolymerization weight ratio = 20/30/20/30, Mw = 9,500, Mn = 5,000) as alkali-soluble resin A pigment dispersion (R) was prepared by treating 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent with a bead mill.
Next, 100 parts by weight of the pigment dispersion (R), (B) 7.5 parts by weight of the resin (B-1) as the alkali-soluble resin, and (C) 7.5 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer (D) 3 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator, and 150 parts by weight of ethyl 3-ethoxypropionate as a solvent A liquid composition (R1) was prepared by mixing 25 parts by weight of propylene glycol monomethyl ether acetate.

Pattern formation The liquid composition (R1) was applied on the surface of a glass substrate using a spin coater, and then prebaked at 90 ° C. for 2 minutes to form a coating film having a thickness of 2.5 μm. Thereafter, the substrate was cooled to room temperature, and the coating film on the substrate was exposed to the coating film on the substrate through a photomask at an exposure amount of 1,000 J / m ² using a high pressure mercury lamp. Thereafter, a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. is discharged onto the coating film on the substrate at a development pressure of 2 kgf / cm ² (nozzle diameter 1 mm) to perform shower development for 60 seconds, and then 220 ° C. Was post-baked for 30 minutes to form a pixel array in which red line and space patterns were arranged on the substrate.

When the pixel array on the evaluation substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern. Further, a pattern with a line width of 30 μm was formed with good linearity.

Example 2
Preparation of liquid composition and pattern formation A liquid composition (R2) was prepared in the same manner as in Example 1 except that the resin (B-2) was used instead of the resin (B-1).
Next, a pixel array in which red line and space patterns are arranged on the substrate is formed in the same manner as in Example 1 except that the liquid composition (R2) is used instead of the liquid composition (R1). did.

When the pixel array on the evaluation substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern. Further, the pattern having a line width of 50 μm was formed with good linearity.

Comparative Example 1
Preparation of Liquid Composition and Pattern Formation A liquid composition (R3) was prepared in the same manner as in Example 1 except that the resin (β-1) was used instead of the resin (B-1).
Next, a pixel array in which red line and space patterns are arranged on the substrate is formed in the same manner as in Example 1 except that the liquid composition (R3) is used instead of the liquid composition (R1). did.

When the pixel array on the evaluation substrate was observed with an optical microscope, a development residue was observed on the unexposed substrate. Further, although a pattern with a line width of 30 μm could be formed, there was an undeveloped portion and the linearity was poor.

Example 3
Preparation of Liquid Composition (A) CI Pigment Green 36 / CI Pigment Yellow 138 / CI Pigment Yellow 150 = 50/40/10 (weight ratio) as a colorant 15 parts by weight, Dispersbyk-2001 4 parts by weight as a dispersant (In terms of solid content), (B) methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/10 /) as an alkali-soluble resin 20/10/35/10, Mw = 6,000, Mn = 3,000) and 76 parts by weight of propylene glycol monomethyl ether acetate as a solvent were treated in the same manner as in Example 1 to obtain a pigment dispersion. (G) was prepared.
Next, 100 parts by weight of the pigment dispersion (G), (B) 7 parts by weight of the resin (B-1) as the alkali-soluble resin, (C) 8 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (D ) 3 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator, 0.1 part by weight of malonic acid as an additive, and 3-methoxy as a solvent 125 parts by weight of butyl acetate and 50 parts by weight of propylene glycol methyl ether acetate were mixed to prepare a liquid composition (G1).

Formation of Pattern Next, pixels in which green line and space patterns are arranged on the substrate in the same manner as in Example 1 except that the liquid composition (G1) is used instead of the liquid composition (R1). An array was formed.

When the pixel array on the evaluation substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern. Further, a pattern with a line width of 30 μm was formed with good linearity.

Comparative Example 2
Preparation of Liquid Composition and Pattern Formation A liquid composition (G2) was prepared in the same manner as in Example 3 except that the resin (β-1) was used instead of the resin (B-1).
Next, a pixel array in which green line and space patterns are arranged on the substrate is formed in the same manner as in Example 1 except that the liquid composition (G2) is used instead of the liquid composition (R1). did.

When the pixel array on the evaluation substrate was observed with an optical microscope, a development residue was observed on the unexposed substrate. Further, although a pattern with a line width of 30 μm could be formed, there was an undeveloped portion and the linearity was poor.

Example 4
Preparation of liquid composition (A) 15 parts by weight of 95/5 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a colorant, and 4 parts by weight of Disperbyk-2001 as a dispersant (in terms of solid content) ), (B) methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/10/20/10 / 35/10, Mw = 6,000, Mn = 3,000), and 76 parts by weight of propylene glycol monomethyl ether acetate as a solvent were treated in the same manner as in Example 1 to obtain a pigment dispersion (B). Prepared.
Subsequently, 100 parts by weight of the pigment dispersion (B), (B) 6 parts by weight of the resin (B-1) as the alkali-soluble resin, (C) 9 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (D ) 3 parts by weight of 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one as a photopolymerization initiator, and A-60 (trade name, non-ionic interface manufactured by Kao Corporation) as an additive Activating agent) 0.5 parts by weight, and 150 parts by weight of ethyl 3-ethoxypropionate and 25 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed to prepare a liquid composition (B1).

Formation of Pattern Next, pixels in which blue line and space patterns are arranged on the substrate in the same manner as in Example 1 except that the liquid composition (B1) is used instead of the liquid composition (R1). An array was formed.

When the pixel array on the evaluation substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern. Further, a pattern with a line width of 30 μm was formed with good linearity.

Comparative Example 3
Preparation of Liquid Composition and Pattern Formation A liquid composition (B2) was prepared in the same manner as in Example 4 except that the resin (β-1) was used instead of the resin (B-1).
Next, a pixel array in which blue line and space patterns are arranged on the substrate is formed in the same manner as in Example 1 except that the liquid composition (B2) is used instead of the liquid composition (R1). did.

When the pixel array on the evaluation substrate was observed with an optical microscope, a development residue was observed on the unexposed substrate. Further, although a pattern with a line width of 30 μm could be formed, there was an undeveloped portion and the linearity was poor.

Example 5
Preparation of liquid composition (A) 20 parts by weight of carbon black (manufactured by Mikuni Dye Co., Ltd.) as a colorant, 2 parts by weight of Disperbyk-2001 (in terms of solid content) as a dispersant, (B) methacrylic acid as an alkali-soluble resin / Ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000) 4 parts by weight and 74 parts by weight of 3-methoxybutyl acetate as a solvent were treated in the same manner as in Example 1 to prepare a pigment dispersion (BK).
Next, 100 parts by weight of pigment dispersion (BK), (B) resin (B as alkali-soluble resin)
-3) 8 parts by weight, (C) 7 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2-benzyl-2-dimethylamino-1- (4-morpholino as a photopolymerization initiator 4 parts by weight of phenyl) butan-1-one, 0.5 part by weight of A-60 (trade name, manufactured by Kao Corporation) as an additive, and 125 parts by weight of propylene glycol methyl ether acetate as a solvent A liquid composition (BK1) was prepared by mixing 50 parts by weight of cyclohexanone.

Formation of Pattern Next, pixels in which black line and space patterns are arranged on the substrate in the same manner as in Example 1 except that the liquid composition (BK1) is used instead of the liquid composition (R1). An array was formed.

When the pixel array on the evaluation substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern. Further, a pattern with a line width of 30 μm was formed with good linearity.

Comparative Example 4
Preparation of Liquid Composition and Pattern Formation A liquid composition (BK2) was prepared in the same manner as in Example 5 except that the resin (β-2) was used instead of the resin (B-3).
Next, a pixel array in which black line and space patterns are arranged on the substrate is formed in the same manner as in Example 1 except that the liquid composition (BK2) is used instead of the liquid composition (R1). did.

When the pixel array on the evaluation substrate was observed with an optical microscope, a development residue was observed on the unexposed substrate. Further, although a pattern with a line width of 30 μm could be formed, there was an undeveloped portion and the linearity was poor.

Example 6
Preparation of liquid composition 100 parts by weight of pigment dispersion (BK), (B) 8 parts by weight of resin (B-3) as alkali-soluble resin, (C) 7 parts by weight of dipentaerythritol hexaacrylate as polyfunctional monomer (D) Ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) 2 parts by weight, A-60 (trade name, nonionic surfactant manufactured by Kao Corporation) as an additive, 0.5 parts by weight, and solvent A liquid composition (BK3) was prepared by mixing 125 parts by weight of propylene glycol methyl ether acetate and 50 parts by weight of cyclohexanone.

Formation of Pattern Next, pixels in which black line and space patterns are arranged on the substrate in the same manner as in Example 1 except that the liquid composition (BK3) is used instead of the liquid composition (R1). An array was formed.

When the pixel array on the evaluation substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no scum or chipping was observed on the edge of the pixel pattern. Further, a pattern having a line width of 15 μm was formed with good linearity.

Claims (3)

In the radiation-sensitive composition for forming a colored layer, comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. The resin has a structural unit represented by the following formula (1) and / or a structural unit represented by the following formula (2), and a radical polymerization initiator represented by the following formula (3) is an essential component. Including an addition polymerization polymer having a carboxyl group at least at one end of a polymer chain , which is produced by radical polymerization in the presence of a radical polymerization initiator having one or more carboxyl groups in the molecule. A radiation-sensitive composition for forming a colored layer.

(In the formula, R ¹ represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.)

(In the formula, each R ² independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group.)

(In formula, each R < ³ > shows a methylene group, a C2-C12 alkylene group, or a C6-C12 arylene group mutually independently.)   The color filter which has a colored layer formed using the radiation sensitive composition for colored layer formation of Claim 1. A color liquid crystal display device comprising the color filter according to claim 2 .