KR101705894B1 - Radiation-sensitive composition for forming colored layer, color filter and color liquid crystal display device - Google Patents

Abstract

The present invention provides a radiation sensitive composition capable of forming a pixel and a black matrix which are excellent in adhesion to a substrate and have high precision and fine pattern shape.

The radiation-sensitive composition for forming a coloring layer of the present invention comprises (A) a colorant, (B) an alkali-soluble resin, (C) a monomer having two or more radically polymerizable unsaturated bonds, (D) a radiation- E) a specific phenolic compound.

A radiation-sensitive composition for forming a colored layer, a color filter, a color liquid crystal display element, a plastic, a spirobiindane, a spirobindene

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation-sensitive composition for forming a coloring layer, a color filter, and a color liquid crystal display (hereinafter referred to as a " color filter "

The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter and a liquid crystal display element, and more particularly to a radiation-sensitive composition for forming a colored layer useful for a color filter used in a transmission type or reflection type color liquid crystal display, , A color filter having a coloring layer formed using the radiation sensitive composition, and a color liquid crystal display device having the color filter.

A method of forming a color filter using a coloring and radiation-sensitive composition, comprising the steps of: forming a coating film of a coloring and radiation-sensitive composition on a substrate or on a substrate on which a light-shielding layer of a desired pattern has been formed in advance; (Refer to, for example, Patent Documents 1 and 2 below) of irradiating radiation (hereinafter referred to as "exposure"), developing and removing the unexposed portions, and post-baking .

In recent years, there has been a demand for a screen that is brighter for monitors and televisions and has good color reproducibility, and it is necessary to increase the content of colorants, especially pigments, contained in the radiation sensitive composition, along with the improvement of the brightness of the backlight (Non-Patent Document 1). Further, the liquid crystal monitor screen and the liquid crystal television screen tend to be finer, and the number of pixels per unit area on the screen tends to increase. For this reason, it is required that the radiation sensitive composition is capable of forming a finer pattern than both for forming a black matrix and for forming a pixel.

With respect to this demand, for example, Patent Document 3 discloses that a pattern having a high resolution can be formed by containing an alkali-soluble resin having a specific structure in a radiation-sensitive composition. However, in the so-called negative-type radiation-sensitive composition, since the line width of a pattern to be formed becomes thicker than the designed dimension of a photomask due to the influence of diffracted light at the time of proxymith exposure, a problem that a fine pattern having a desired line width can not be obtained there was.

On the other hand, as a method for resolving the pattern line width of the negative-tone radiation-sensitive composition, for example, there is a method of reducing the amount of exposure and enhancing the developing conditions to reduce the content of the radiation- Or a method of containing a polymerization inhibitor in the radiation sensitive composition is known. However, any method tends to cause defects, peeling, and undercutting of the pattern at the time of development. In particular, when the content of the coloring agent contained in the radiation sensitive composition is high, it can not be applied at all.

[Patent Document 1] JP-A-2-144502

[Patent Document 2] JP-A-3-53201

[Patent Document 3] Japanese Unexamined Patent Publication No. 2004-205862

[Non-Patent Document 1] Tadakazu Murakami "New Development of Front Backlight for LCD ", First Edition, Toray Research Center Co., Ltd., September 2002

It is an object of the present invention to provide a method for forming a pixel and a black matrix which are excellent in adhesion to a substrate and have high precision and fine pattern shape even when the content of the coloring agent contained in the radiation sensitive composition is high, And the pattern line width is not thickened even when the coloring layer is formed.

It is also an object of the present invention to provide a color filter comprising a coloring layer formed of the radiation sensitive composition for forming a coloring layer and a color liquid crystal display device comprising the color filter.

In view of the above circumstances, the present inventors have conducted intensive studies and have found that the problems described above can be solved by containing a phenolic compound having a specific structure in the radiation-sensitive composition for forming a colored layer, It came.

(D) a radiation-sensitive radical-generating agent; and (E) a radiation-sensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a monomer having two or more radically polymerizable unsaturated bonds, , A phenolic compound having a platelet skeleton, a phenolic compound having a spirobiindane skeleton, and a phenolic compound having a spirobiindene skeleton. And to provide a radiation-sensitive composition for forming a colored layer.

기(단, k는 0 내지 4의 정수이다)를 나타내며, R² 및 R³은 서로 동일하거나 상이할 수 있고, 수소 원자, 탄소수 6 이하의 알킬기, 탄소수 6 이하의 아실기, 페닐기, 나프틸기 또는 -(CH₂)x-COOZ기를 나타내며, m, n, p 및 q는 0 이상의 정수이고, m+n≤5, p+q≤5, n+q≥1의 관계를 만족시킨다〕[In the formula 1, R ¹ is an alkoxy group of a hydrogen atom, an alkyl group having 4 or less, carbon number of 4 or less, a phenyl group, a naphthyl group, or - represents a group _{(CH 2) x-COOZ,} R 1 to a plurality of presence are the same with each other or Z may be the same or different from each other, x is an integer of from 0 to 4, and A is an integer of from 0 to 4, and Z is an alkoxyalkyl group, a cyclic ether group, a vinyloxyalkyl group or a t-alkoxycarbonylalkyl group, is a single bond, -S- group, -O- group, -CO- group, -COO- group, -SO- group, -SO ₂ - ^{group, -C (R 2) (R} 3) - group, or

(Wherein k is an integer of 0 to 4), R ² and R ³ may be the same or different and each represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, an acyl group having 6 or less carbon atoms, a phenyl group, a naphthyl group or - (CH ₂₎ represents an x-COOZ, and m, n, p and q are an integer of 0 or more, it satisfies the relationship of m + n≤5, p + q≤5, n + q≥1]

Wherein R ¹ represents the same group as R ¹ in formula (1), R ⁴ represents the same group as R ² in formula (1), m, n, p, q, r and s are integers of 0 or more, m + n? 5, p + q? 5, r + s? 5, n + q + s?

Wherein R ¹ represents the same group as R ¹ in formula (1), R ⁴ represents the same group as R ² in formula (1), two R ⁴ may be the same as or different from each other, M + n? 5, p + q? 5, r + s? 5, t + u ?, where m, n, p, q, r, s, t and u are integers of 0 or more. 5, n + q + s + u? 1]

[In the formula 4, R ¹ represents a group the same as R ¹ of formula 1, R ^2, R ³ and R ⁴ each represent the same group with the general formula (I) of R ^2, R ³ and R ⁴ of formula 2, m, p + q? 5, r + s? 5, t + u? 4, n + q + s + u where n, p, q, r, s, t and u are integers of 0 or more. 1 >

Wherein R ¹ , R ² and R < ³ > is R < 1 ^> , R < ² & Represents the same groups as R ^3, m, n, and p, q, r and s is an integer equal to or greater than 0, m + n≤5, p + q≤4, the r + s≤5, n + q + s≥2 And l represents an integer of 1 to 5]

The present invention also provides a color filter having a colored layer formed using the radiation sensitive composition for forming a colored layer, and a color liquid crystal display device having the color filter.

By using the radiation-sensitive composition containing the component (E) of the present invention, even when the content of the coloring agent contained in the radiation-sensitive composition is high, it is possible to provide a high- A black matrix can be formed, and the pattern line width does not become thick even in the proximity exposure.

Therefore, the color filter of the present invention is useful for, for example, a transmissive or reflective color liquid crystal display device, a color image pickup tube device, a color sensor and the like.

(Radiation-sensitive composition for forming colored layer)

The term "coloring layer" in the radiation-sensitive composition for forming a coloring layer (hereinafter simply referred to as "radiation-sensitive composition") of the present invention means a layer containing a pixel and / or a black matrix used in a color filter do.

Hereinafter, constituent components of the radiation-sensitive composition for forming a colored layer of the present invention will be described.

- (A) Colorant -

The (A) coloring agent in the present invention is not particularly limited and may be any one of organic pigments and inorganic pigments.

As the organic pigment, for example, a compound classified as a pigment in a color index (CI, published by The Society of Dyers and Colourists), specifically, a color index (CI) number given below .

C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 211;

 C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 68, C.I. Pigment Orange 70, C.I. Pigment Orange 71, C.I. Pigment Orange 72, C.I. Pigment Orange 73, C.I. Pigment Orange 74;

 C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 5, C.I. Pigment Red 17, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 41, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 209, C.I. Pigment Red 214, C.I. Pigment Red 220, C.I. Pigment Red 221, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 262, C.I. Pigment Red 264, C.I. Pigment Red 272;

 C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 38;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, C.I. Pigment Blue 80;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58;

C.I. Pigment Brown 23, C.I. Pigment Brown 25;

C.I. Pigment Black 1, C.I. Pigment Black 7.

In the present invention, the organic pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, spinach (red iron oxide (III)), cadmium, Green, cobalt green, umber, titanium black, synthetic iron black, and carbon black.

These colorants may be used by modifying the surface of the particles with a polymer as desired. Examples of the polymer for modifying the particle surface of the pigment include a polymer described in Japanese Patent Application Laid-Open No. 8-259876, and a commercially available polymer or oligomer for dispersing various pigments. Examples of the method of covering the surface of a carbon black with a polymer are disclosed in, for example, Japanese Patent Application Laid-Open Nos. 9-71733, 9-95625, 9-124969, .

These coloring agents may be used alone or in combination of two or more.

When the radiation sensitive composition of the present invention is used for the formation of a pixel, since the pixel requires high precision and fine color development and heat resistance, the colorant (A) is preferably a colorant having high colorability and high heat resistance, , Specifically, an organic coloring agent is preferable, and an organic pigment is particularly preferably used.

On the other hand, when the radiation sensitive composition of the present invention is used in the formation of a black matrix, the black matrix is required to have a light shielding property. Therefore, an organic pigment or carbon black is preferably used as the colorant (A).

According to the radiation sensitive composition of the present invention, even when the content of the coloring agent is 30 wt% or more of the total solid content of the radiation sensitive composition, it is possible to form a pattern which does not cause defect or peeling and does not increase the line width. In the present invention, the upper limit of the content of the colorant is preferably 60% by weight or less, particularly preferably 50% by weight or less, based on the total solid content of the radiation sensitive composition, from the viewpoint of securing developability. Here, the solid content is a component other than the solvent described later.

The colorant in the present invention can be used together with a dispersant and a dispersion auxiliary agent if desired.

As the dispersing agent, for example, a suitable dispersing agent such as cationic, anionic, nonionic or amphoteric can be used, but a polymer dispersant is preferable. Specific examples thereof include alkylammonium salts or phosphoric acid ester salts of modified acrylic copolymers, acrylic copolymers, polyurethanes, polyesters, and polymeric copolymers, and cationic comb-like graft polymers. Here, the cationic comb type graft polymer refers to a polymer having a structure in which two or more branched polymers are graft-bonded to one molecule of a stem polymer having a plurality of basic groups (cationic functional groups), and examples thereof include a styrene polymer- And polymers in which the polymer is composed of ring-opening polymers of? -Caprolactone. Among these dispersants, a modified acrylic copolymer, a polyurethane, and a cationic comb-like graft polymer are preferable.

Such dispersants are commercially available, for example, modified acrylic copolymers such as Disperbyk-2000 and Disperik-2001 (manufactured by BYK), polyurethane, disperse- DISPERBY-167, DISPERBIC-170, DISPERBY-182 (manufactured by BYK), EFKA4046 (manufactured by Ciba Specialty Chemicals) (Manufactured by Lubrizol Corporation), Azisper PB821, Ajisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as the cationic comb-type graft polymer, And the like.

These dispersants may be used alone or in combination of two or more. The content of the dispersant is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, and particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of (A) the colorant. In this case, if the content of the dispersing agent exceeds 100 parts by weight, developability and the like may be damaged.

Examples of the dispersion aid include blue pigment derivatives and yellow pigment derivatives, and specific examples thereof include copper phthalocyanine derivatives.

- (B) Alkali-soluble resin -

The alkali-soluble resin (B) contained in the radiation-sensitive composition of the present invention is not particularly limited as long as it is soluble in the alkali developing solution used in the developing treatment step in forming the colored layer, A hydroxyl group and the like. Among them, it is preferable to contain a polymer having a carboxyl group, particularly a polymer having a repeating unit represented by the following formula (6) (hereinafter referred to as "polymer (B1)") and a repeating unit represented by the following formula (Hereinafter referred to as "polymer (B2)").

(Wherein R ⁵ represents a hydrogen atom or a methyl group)

(Wherein R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X is a monovalent organic group having an acryloyl group or a methacryloyl group, a vinyl group or a 1- Methyl vinyl group, Y represents a divalent organic group, and h represents an integer of 1 to 5)

In the general formula (7), R ⁶ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R ⁷ and R ⁸ are preferably a hydrogen atom. h is preferably 1.

In the formula (7), the monovalent organic group having an acryloyl group or a methacryloyl group of X is preferably a group represented by the following formula (X-1) or (X-2). As X in the general formula (7), a vinyl group or a 1-methylvinyl group is preferable.

≪ General Formula (X-1)

(Wherein R ¹⁶ represents a hydrogen atom or a methyl group, i represents an integer of 2 to 5, j represents an integer of 1 to 10, and "* "

<Formula X-2>

(Wherein R ¹⁷ represents a hydrogen atom or a methyl group, R ¹⁸ represents a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms, a cyclohexane-1,2-diyl group or a 1,2- "*" Indicates a combined hand)

Examples of Y in formula (7) include a methylene group, an alkylene group having 2 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms (provided that these alkylene and alkenylene groups may be interrupted by an oxygen atom on the way) A cyclohexanediyl group or an arylene group having 6 to 12 carbon atoms (provided that the arylene group may have a carboxyl group or an acid anhydride group), and a methylene group, an ethylene group, a 1,3-propylene group, 1,2-propenylene group, 1,3-propenylene group, 2,3-propenylene group, cyclohexane-1,2-diyl group, 4-cyclohexene-1,2 A di-yl group, a 1,2-phenylene group, a biphenyl-2,2'-diyl group, or a -CH ₂ -O-CH ₂ - group.

The alkali-soluble resin (B) contained in the radiation-sensitive composition of the present invention may contain, in addition to the repeating units represented by the above formula (6) or (7), repeating units represented by the following formula (8) and repeating units represented by the following formula Is preferably a polymer having at least one repeating unit selected from the group consisting of

(Wherein R ⁹ represents a straight, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms)

(Wherein R ¹⁰ to R ¹⁵ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group)

Examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms represented by R ^{9 in} the above formula (8) include a methyl group, ethyl group, n-propyl group, i-propyl group, n- An n-hexyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, a n-decyl group, an n-undecyl group, An acyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the aryl group having 6 to 12 carbon atoms for R ⁹ include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group and 2-naphthyl group.

As R ⁹ in the formula (8), a cyclohexyl group, a phenyl group and the like are preferable, and a phenyl group is particularly preferable.

Examples of the halogen atom represented by R ¹⁰ to R ^{15 in} the above formula (9) include a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

In the general formula (9), it is preferable that all of R ¹⁰ to R ¹⁵ are a hydrogen atom, or R ¹² is a chlorine atom, a hydroxyl group or a hydroxymethyl group, and R ¹⁰ and R ¹¹ and R ¹³ to R ¹⁵ are both hydrogen atoms , And it is more preferable that all of R ¹⁰ to R ¹⁵ are hydrogen atoms.

In the polymer (B1), the repeating unit represented by the above formula (6) is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, based on the total repeating units of the polymer (B1). In the polymer (B2), the repeating unit represented by the formula (7) is preferably 5 to 80% by weight, more preferably 10 to 60% by weight, based on the total repeating units of the polymer (B2). When the proportion of the repeating unit represented by the general formula (6) or (7) in the alkali-soluble resin (B) is in this range, the developability of the radiation-sensitive composition containing the same is better, Which is preferable.

The polymer (B1) and the polymer (B2) in the present invention have a repeating unit represented by the above general formula (8) in the range of 50% by weight or less based on the total repeating units of the polymer (B1) or the polymer , More preferably in the range of 5 to 40 wt%. It is preferable that the polymer (B1) and the polymer (B2) have a repeating unit represented by the above formula (9) in a range of 60% by weight or less based on the total repeating units of the polymer (B1) or the polymer (B2) And more preferably in the range of 5 to 40% by weight. The polymer (B1) and the polymer (B2) may have both of the repeating unit represented by the formula (8) and the repeating unit represented by the formula (9). In this case, Is preferably 80% by weight or less, more preferably 10 to 70% by weight based on the total repeating units of the polymer (B2). In this case, the respective content ratios of the repeating units represented by the above formula (8) or the above-mentioned repeating units represented by the above formula (9) are preferably within the aforementioned ranges.

When the content ratio of the repeating unit represented by the formula (8) and the repeating unit represented by the formula (9) in the polymer (B1) and the polymer (B2) is in the above range, there is an advantage that the adhesion to the substrate is further improved .

The polystyrene reduced weight average molecular weight (hereinafter also referred to as "Mw") of the alkali soluble resin (B) in the present invention measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) And particularly preferably from 3,000 to 20,000.

The polystyrene reduced number average molecular weight (hereinafter also referred to as "Mn") of the alkali-soluble resin (B) in the present invention measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) More preferably from 3,000 to 20,000.

In this case, if the Mw is less than 1,000, the residual film ratio or the like of the resulting film may deteriorate, the pattern shape, heat resistance and the like may be damaged or the electrical characteristics may deteriorate. On the other hand, if it exceeds 45,000, Or dry foreign matter may be easily generated during application by the slit nozzle method.

The polymer (B1) can be obtained by, for example, radical polymerizing compounds containing (meth) acrylic acid, 2,2'-azobisisobutyronitrile, 2,2'-azobis Dimethylvaleronitrile), and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) in the presence of a radical polymerization initiator.

The polymer (B1) can be purified through the reprecipitation method using two or more kinds of organic solvents having different polarities after the radical polymerizing compound is subjected to radical polymerization as described above. That is, after the polymerization, the solution in the good solvent is poured into a precipitant (poor solvent) in a large amount (normally, 5 to 10 times the volume of the polymer solution) after removing insoluble impurities by filtration or centrifugation if necessary, &Lt; / RTI &gt; At that time, of the impurities remaining in the polymer solution, the impurities soluble in the precipitant remain in the liquid phase and are separated from the purified polymer (B1).

Examples of the combination of the positive solvent and the precipitant used in this reprecipitation method include cyclohexanone / n-hexane, propylene glycol monoethyl ether / n-hexane, cyclohexanone / n-heptane, propylene glycol monoethyl ether / n-heptane and the like.

The polymer (B1) can be obtained by copolymerizing the radical polymerization initiator and the pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, pyrazole-1-dithiocarboxylic acid benzyl ester, tetraethylthiuram disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis Feed, bis (5-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis In the presence of a molecular weight control agent serving as an initiator such as diisopropylbenzyl disulfide or bisthiobenzoyl disulfide in an inert solvent at a reaction temperature of usually 0 to 150 ° C, preferably 50 to 120 ° C, Or by radical polymerization.

Examples of other radical polymerizable compounds that are preferably copolymerized with (meth) acrylic acid in the polymer (B1) include compounds represented by the following formula (8-1) (hereinafter also referred to as " (Hereinafter also referred to as a " compound (b3) ") other than the compound (b1) and the compound (b2) ). In the polymer (B1), a polymer (B1) obtained by copolymerizing a radically polymerizable compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate or the like is added to 2- It is also possible to introduce a polymerizable unsaturated bond into the side chain of the polymer by reacting an unsaturated isocyanate compound such as oxyethyl isocyanate.

<Formula 8-1>

(Wherein, R ⁹ is R ⁹ and agreement in the above formula (8))

<Formula 9-1>

(In the formula, R ¹⁰ to R ¹⁵ is R ¹⁰ to R ¹⁵ and consent for Formula 9)

The compound (b1) induces the repeating unit represented by the formula (8) in the alkali-soluble resin (B). Specific examples of the compound (b1) include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Nt- -Hexyl maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-1-naphthyl maleimide and the like. Among these compounds (b1), N-cyclohexylmaleimide and N-phenylmaleimide are preferable, and N-phenylmaleimide is particularly preferable. In the polymer (B1), the compound (b1) may be used alone or in combination of two or more.

The compound (b2) induces the repeating unit represented by the above formula (9) in the alkali-soluble resin (B). Specific examples of the compound (b2) include, for example, acenaphthylene, 5-chloroacenaphthylene, 5-hydroxymethylacenaphthylene and 5-hydroxyacenaphthylene. Of these compounds (b2), acenaphthylene and 5-chloroacenaphthylene are preferable, and acenaphthylene is particularly preferable. In the polymer (B1), the unsaturated compound (b2) may be used alone or in admixture of two or more.

As the compound (b3), for example,

Unsaturated monocarboxylic acids such as crotonic acid,? -Chloroacrylic acid and cinnamic acid;

Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid;

Mono [(meth) acryloyloxyalkyl] monovalent monocarboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] Esters;

ω-carboxypolycaprolactone mono (meth) acrylate; mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals;

vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m- Unsaturated phenols such as propenyl phenol;

2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl- Unsaturated naphthols such as naphthol;

Styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Aromatic vinyl compounds such as ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

Indene such as indene and 1-methylindene;

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2- (Meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxypropyl Alkylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yl (meth) acrylate, 2 Unsaturated carboxylates such as hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, and ethylene oxide-modified (meth) Acid esters;

(Meth) acrylate, 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl Unsaturated carboxylic acid aminoalkyl esters such as 3-dimethylaminopropyl (meth) acrylate;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;

(Meth) acrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide;

Unsaturated amides such as (meth) acrylamide,? -Chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

And 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.

Examples of the compound (b3) in the polymer (B1) include mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals Unsaturated carboxylic acid esters and macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain are preferable, and mono [2- (meth) acryloyl succinic acid mono [2- Isopropenylphenol, styrene,? -Methylstyrene, methyl (meth) acrylate, n-butyl (meth) acrylate,? -Carboxypolycaprolactone mono (Meth) acrylate, glycerol mono (meth) acrylate, 4-ethylhexyl (meth) acrylate, 2-hydroxyethyl Hydroxyphenyl (meth) (Meth) acrylate, para-cumylphenol, ethylene oxide modified (meth) acrylate, polystyrene macromonomer, and polymethyl methacrylate macromonomer.

In the polymer (B1), the compound (b3) may be used alone or in combination of two or more.

The polymer (B2) is a polymer of a radically polymerizable compound containing a compound represented by the following formula (7-1) (hereinafter also referred to as "compound (b4)") (hereinafter also referred to as a "styrene epoxide polymer" (Hereinafter referred to as "unsaturated monocarboxylic acid (X)") is then added to the compound represented by the following formula (7-2) ) ").

&Lt; Formula

^{(Wherein, R 6, R 7, R} 8 , and h is the R ^6, R ^7, R ⁸ and h and consent for Formula 7, respectively)

<Formula 7-2>

(Wherein X is synonymous with X in the above formula (7)).

<Formula 7-3>

(Wherein Y is synonymous with Y in the above formula (7)).

Specific examples of the compound (b4) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,? -Methyl- Methyl-m-vinylbenzyl glycidyl ether,? -Methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethyl styrene, 2,4-diglycidyl Glycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyl, 2,6-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, Trimethylolpropane trimethylolpropane, trimethylolpropane trimethylolpropane trimethylolpropane trimethoxymethylstyrene, oxymethylstyrene, 2,3,6-triglyldoxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene and 2,4,6-triglycidyloxymethylstyrene. Among these compounds (b4), o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether are preferable, and p-vinyl benzyl glycidyl ether is particularly preferable. In the polymer (B2), the compound (b4) may be used alone or in combination of two or more.

Examples of other radically polymerizable compounds which are preferably copolymerized with the compound (b4) in the styrene epoxy polymer include the above-mentioned compounds (b1), (b2) and (b3). In the styrene-epoxy polymer, the compound (b1) and the compound (b2) are preferably the same as those exemplified for the polymer (B1). As the compound (b3) in the styrene epoxy polymer, an aromatic vinyl compound, an unsaturated carboxylic acid ester, and a macromonomer having a mono (meth) acryloyl group at the terminal of the polymer molecular chain are preferable, and styrene, (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (Meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, ethylene oxide modified (meth) acrylate of para-cumylphenol, polystyrene macromonomer and polymethyl methacrylate macromonomer .

In the styrene epoxy polymer, the compound (b1), the compound (b2) and the compound (b3) may be used either individually or in combination of two or more.

The styrene epoxy polymer can be prepared in the same manner as the polymer (B1), and its Mw and Mn can be appropriately set in accordance with the desired Mw and Mn of the desired (B) alkali-soluble resin.

The unsaturated carboxylic acid (X) can be appropriately selected depending on the kind of the desired X in the formula (7). Preferred unsaturated carboxylic acids (X) include, for example, acrylic acid, methacrylic acid, omega -carboxy-polycaprolactone monoacrylate, omega -carboxy-polycaprolactone monomethacrylate, 2- acryloyloxyethyl succinic acid , 2-methacryloyloxyethylsuccinic acid, and the like. In the ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate, the number of repeating units of polycaprolactone is preferably 1 to 10, more preferably 2 to 5. Among the above unsaturated carboxylic acids (X), acrylic acid or methacrylic acid is more preferable because it is rich in reactivity, and acrylic acid is particularly preferable.

The unsaturated carboxylic acid (X) may be used alone or in admixture of two or more.

The addition reaction of the unsaturated monocarboxylic acid (X) to the styrene epoxy polymer can be carried out according to a known method. The amount of the unsaturated monocarboxylic acid (X) to be used is preferably in the range of 0.7 to 1.3 equivalents, more preferably 0.9 to 1.2 equivalents, per one equivalent of the epoxy group of the styrene epoxide polymer.

The polybasic acid anhydride (y) can be appropriately selected according to the kind of Y desired in the formula (7). Examples of preferred polybasic acid anhydrides (y) include maleic anhydride, maleic anhydride, citraconic anhydride, succinic anhydride, anhydroglutaric acid, anhydroglutaconic acid, itaconic anhydride, diglycolic anhydride, phthalic anhydride, Hexane-1,2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, and anhydrous diphenic acid. Among them, succinic anhydride, glutaric anhydride, phthalic anhydride or 4-cyclohexene-1,2-dicarboxylic acid anhydride are particularly preferred because they are rich in reactivity.

The addition reaction of the polybasic acid anhydride (y) to the styrene epoxy polymer can be carried out according to a known method. The addition amount of the polybasic acid anhydride (y) is preferably in the range of 0.2 to 1.0 equivalent, more preferably 0.4 to 0.9 equivalent, per one equivalent of the epoxy group of the styrene epoxy polymer.

In the present invention, the polymer (B1) and the polymer (B2) may be used alone or in combination of two or more. As the alkali-soluble resin, for example, a copolymer of the (meth) acrylic acid and the compound (b3) may be used together with the polymer (B1) and / or the polymer (B2).

In the present invention, the content of the alkali-soluble resin is usually from 10 to 1,000 parts by weight, particularly preferably from 20 to 500 parts by weight, per 100 parts by weight of (A) the colorant. In this case, if the content of the alkali-soluble resin is less than 10 parts by weight, for example, alkali developability may be deteriorated, or residual or background contamination may occur on the substrate of the unexposed portion or the light-shielding layer, , The concentration of the coloring agent is relatively lowered, so that it may be difficult to achieve the intended color density as the thin film.

- (C) a monomer having two or more radically polymerizable unsaturated bonds,

As the monomer having two or more radically polymerizable unsaturated bonds in the present invention (hereinafter also referred to as "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, trimethylol propane, pentaerythritol and dipentaerythritol, and dicarboxylic acid-modified products thereof;

(Meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin and spirane resin;

Di (meth) acrylates of both end hydroxylated polymers such as end-capped hydroxypoly-1,3-butadiene, end-capped hydroxypolyisoprene, and end-capped hydroxypolycaprolactone,

Tris [2- (meth) acryloyloxyethyl] phosphate or

Isocyanuric acid ethylene oxide modified triacrylate, and the like.

Of these polyfunctional monomers, poly (meth) acrylates of polyvalent alcohols having three or more valences or dicarboxylic acid-modified products thereof, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tri Acrylate, pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate , Dipentaerythritol hexamethacrylate, monoesters of pentaerythritol triacrylate with succinic acid, monoesters of pentaerythritol trimethacrylate with succinic acid, copolymers of dipentaerythritol pentaacrylate and succinic acid Monoester, dipentaerythritol penta methacrylate And monoesters of succinic acid and succinic acid. Of these, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate And monoesters of dipentaerythritol pentaacrylate with succinic acid have high strength of the colored layer and excellent surface smoothness of the colored layer and are excellent in surface smoothness on the substrate of the unexposed portion and on the substrate Contamination, membrane residue, and the like are less likely to occur.

The polyfunctional monomers may be used singly or in combination of two or more.

The content of the polyfunctional monomer (C) in the present invention is generally 5 to 500 parts by weight, preferably 20 to 300 parts by weight, per 100 parts by weight of the alkali-soluble resin (B). In this case, if the content of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to be lowered. On the other hand, if the content of the polyfunctional monomer exceeds 500 parts by weight, There is a tendency that background contamination, film residue, and the like tend to occur on the light-shielding layer or the light-shielding layer.

Further, in the present invention, a part of the polyfunctional monomer may be replaced by a monomer having one radically polymerizable unsaturated bond (hereinafter also referred to as "monofunctional monomer").

Examples of the monofunctional monomers include mono (meth) acryloyloxyethyl esters such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (Meth) acryloyloxyalkyl esters, mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -Carboxypolycaprolactone mono (meth) acrylate, N- M-5600 (trade name, manufactured by Toagosei Co., Ltd.) as a commercial product in addition to acryloylmorpholine, N-vinylpyrrolidone and N-vinyl-epsilon -caprolactam.

These monofunctional monomers may be used singly or in combination of two or more. The content of the monofunctional monomer is usually 90% by weight or less, preferably 50% by weight or less based on the total amount of the polyfunctional monomer and the monofunctional monomer. In this case, if the content of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the resulting colored layer may be insufficient.

- (D) Radiation-sensitive radical generator -

The radiation-sensitive radical-generating agent in the present invention initiates the polymerization of the above-mentioned polyfunctional monomer and optionally monofunctional monomer by exposure to radiation such as visible light, ultraviolet light, extra-atom radiation, electron beam, X- Is an active radical-generating compound.

Examples of such a radiation-sensitive radical generator include an acetophenone-based compound, a nonimidazole-based compound, a triazine-based compound, an O-acyloxime-based compound, a benzoin-based compound, and an? -Diketone-based compound.

In the present invention, the radiation-sensitive radical generators may be used alone or in admixture of two or more. Examples of the radiation-sensitive radical generator in the present invention include acetophenone-based compounds, nonimidazole-based compounds, A compound, and an O-acyloxime-based compound.

In the present invention, the general content of the radiation-sensitive radical generator is usually 0.01 to 120 parts by weight, preferably 1 to 100 parts by weight, per 100 parts by weight of the (C) polyfunctional monomer. In this case, if the content of the radiation-sensitive radical generating agent is less than 0.01 part by weight, the curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which colored layer patterns are arranged in a predetermined arrangement. On the other hand, The colored layer formed tends to be easily removed from the substrate at the time of development.

Among the preferred radiation-sensitive radical generators in the present invention, specific examples of the acetophenone-based compound include 2-hydroxy-2-methyl-1-phenylpropan-1- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methyl Benzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- -1-one, 1,2-octanedione, and the like.

Among these acetophenone compounds, particularly 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1- (4-morpholinophenyl) butan-1-one, 1,2-octanedione, and the like desirable.

These acetophenone compounds may be used singly or in combination of two or more.

In the present invention, when the acetophenone-based compound is used as the radiation-sensitive radical generator, the content is usually 0.01 to 80 parts by weight, particularly preferably 1 to 100 parts by weight, per 100 parts by weight of the (C) To 70 parts by weight, more preferably 1 to 60 parts by weight. In this case, when the content of the acetophenone compound is less than 0.01 part by weight, the curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which colored layer patterns are arranged according to a predetermined arrangement. On the other hand, The colored layer formed thereon tends to be easily removed from the substrate at the time of development.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1 , 2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ' , 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis , 6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Among these imidazole-based compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like are preferable, and 2,2'-bis (2-chlorophenyl) -4,4' -1,2'-biimidazole is preferred.

These non-imidazole-based compounds are excellent in solubility in a solvent, do not generate foreign substances such as undissolved products and precipitates, have a high sensitivity and can sufficiently accelerate the curing reaction by exposure with a small energy amount, Since the curing reaction does not occur, the coated film after exposure is clearly divided into the insoluble cured portion of the developer and the uncured portion having high solubility with respect to the developer, whereby the colored layer pattern having no undercut is formed in a predetermined arrangement Therefore, a highly precise fine color filter disposed can be formed.

These imidazole-based compounds may be used alone or in combination of two or more.

In the present invention, when a nonimidazole-based compound is used as the radiation-sensitive radical generator, the content is preferably 0.01 to 40 parts by weight, more preferably 0.01 to 40 parts by weight, per 100 parts by weight of the total amount of the (C) Is 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the content of the imidazole-based compound is less than 0.01 part by weight, the curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which colored layer patterns are arranged in a predetermined arrangement. On the other hand, If the proportion exceeds the above range, there is a tendency that the formed colored layer is likely to come off from the substrate or to cause film roughness on the surface of the colored layer at the time of development.

In the present invention, when a nonimidazole-based compound is used as the radiation-sensitive radical generator, it is preferable to use the hydrogen donor described below in order to further improve the sensitivity.

The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole-based compound by exposure.

The hydrogen donor in the present invention is preferably a mercaptan-based compound or an amine-based compound as defined below.

The mercapanic compound is a compound having a benzene ring or a heterocyclic group as a parent nucleus and having at least 1, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter, Referred to as "mercapan-based hydrogen donor").

The amine compound is a compound having a benzene ring or a heterocyclic ring as a nucleus and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as &Quot; hydrogen donor ").

These hydrogen donors may also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor will be described in more detail.

The mercaptan-based hydrogen donor may have at least one benzene ring or at least one heterocyclic ring, and may have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, a condensed ring may or may not be formed .

Further, in the case where the mercapan-based hydrogen donor has two or more mercapto groups, as long as at least one free mercapto group remains, at least one of the remaining mercapto groups may be substituted with an alkyl, aralkyl or aryl group , And a structural unit in which two sulfur atoms are bonded to each other via a divalent organic group such as an alkylene group or a structural unit in which two sulfur atoms are bonded in the form of disulfide, as long as at least one free mercapto group remains.

Further, the mercapan-based hydrogen donor may be substituted at a position other than the mercapto group by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4- Thiadiazole, 2-mercapto-2,5-dimethylaminopyridine and the like.

Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

The amine-based hydrogen donor may have at least one benzene ring or at least one heterocyclic ring, and may have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, a condensed ring may or may not be formed have.

In addition, the amine-based hydrogen donor may have at least one of the amino groups substituted with an alkyl group or a substituted alkyl group, and may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, . &Lt; / RTI &gt;

Specific examples of such amine-based hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 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'- Phenones are preferred.

In addition, the amine-based hydrogen donor has an action as a sensitizer even in the case of a radical generator other than a nonimidazole-based compound.

In the present invention, the hydrogen donors may be used singly or in admixture of two or more, but it is preferable to use at least one mercaptan-based hydrogen donor and at least one amine-based hydrogen donor in combination, Is difficult to detach from the substrate, and the strength and the sensitivity of the colored layer are high.

Specific examples of the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / (Diethylamino) benzophenone, 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'- Amino) benzophenone. More preferred combinations are 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis (Diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

The weight ratio of the mercaptan-based hydrogen donor and the amine-based hydrogen donor in the combination of the mercaptan-based hydrogen donor and the amine-based 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 nonimidazole-based compound, the content is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight of the total amount of the (C) By weight, particularly preferably 1 to 20 parts by weight. In this case, if the content of the hydrogen donor is less than 0.01 part by weight, the effect of improving the sensitivity tends to be deteriorated. On the other hand, if the content is more than 40 parts by weight, the formed colored layer tends to fall off from the substrate during development.

In addition, the amine-based hydrogen donor can function as a sensitizer when it is used in combination with a radiation-sensitive radical generator other than a non-imidazole-based compound such as an acetophenone-based compound. When the amine-based hydrogen donor is used as a sensitizer, its content is preferably 300 parts by weight or less, particularly preferably 200 parts by weight or less, based on 100 parts by weight of the radiation-sensitive radical generating agent other than the imidazole-based compound More preferably 100 parts by weight or less. However, if the content is too small, it becomes difficult to obtain a sufficient effect. Therefore, the lower limit of the content is preferably 2 parts by weight, more preferably 5 parts by weight.

Specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) ) -4,6-bis (trichloromethyl) -s-triazine, and other triazine compounds having a halomethyl group.

Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.

The triazine-based compounds may be used alone or in combination of two or more.

In the present invention, when the triazine-based compound is used as the radiation-sensitive radical generator, the content is preferably 0.01 to 40 parts by weight, more preferably 1 to 100 parts by weight, per 100 parts by weight of the polyfunctional monomer (C) 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, if the content of the triazine-based compound is less than 0.01 part by weight, the curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged in a predetermined arrangement. On the other hand, The formed colored layer tends to be easily detached from the substrate at the time of development.

Specific examples of the O-acyloxime compound include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) - ethyl-6-benzoyl-9H-carbazole-2-oxo-o-benzoate, 3-yl] -pentane-l, 2-pentane-l, 2-oxan- Acetate, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane- Benzoate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9H-carbazol- Benzoate, 1- [9-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3- yl] -ethan- 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- acetyloxime), ethanone, 1- [9-Ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) Methoxybenzoyl] -9H-carbazol-3-yl] -, 1- (O-acetyloxime).

Among these O-acyloxime compounds, especially 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [ (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime), ethanone, 1- [ -Dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9H-carbazol-3-yl] -, 1- (O-acetyloxime).

The O-acyloxime compounds may be used alone or in combination of two or more.

In the present invention, when the O-acyloxime compound is used as the radiation-sensitive radical generator, the content is preferably 0.01 to 80 parts by weight, more preferably 0.01 to 80 parts by weight, per 100 parts by weight of the polyfunctional monomer (C) Is 1 to 60 parts by weight, particularly preferably 1 to 50 parts by weight. In this case, if the content of the O-acyloxime compound is less than 0.01 part by weight, the curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which colored layer patterns are arranged in a predetermined arrangement. On the other hand, The colored layer formed tends to be easily removed from the substrate at the time of development.

- Component (E) -

The component (E) in the present invention is a compound represented by any one of the above formulas (1) to (5), a phenolic compound having a platbaan skeleton, a phenolic compound having a spirobiindane skeleton and a phenolic compound having a spirobindene skeleton And at least one compound selected from the group consisting of By including such a component, defects, peeling, and undercutting of the pattern do not occur during development, and it is possible to suppress the pattern line width from being larger than the designed dimension of the photomask in the proximity exposure.

In the compound represented by the general formula (1), the group A in the formula is preferably a -CO- group, a methylene group or an isopropylidene group. As R ¹ , a hydrogen atom or an alkyl or alkoxy group having 4 or less carbon atoms is preferable.

Specific examples of the compound represented by the formula (1) include, for example,

(Polyhydroxy) benzophenones such as 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone , 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone, 2,4,6,3', 4 ', 5'-hexahydroxybenzophenone, 3,4,5,3', 4 ', 5'-hexahydroxybenzophenone and the like;

As the bis (hydroxyphenyl) alkane, bis (p-hydroxyphenyl) methane and the like;

Examples of the bis (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2,2- -Trihydroxyphenyl) propane, and the like.

In the formula (2), R ¹ is preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R ⁴ is preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms.

Specific examples of the compound represented by the general formula (2) include, for example,

Tri (p-hydroxyphenyl) ethane, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 2- [Bis {(5-isopropyl-4-hydroxy-2-methyl) phenyl} methyl] phenol.

In the compound represented by the general formula (3), the group A in the formula is preferably a methylene group. In the formula, R ¹ is preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R ⁴ is preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms.

Specific examples of the compound represented by the general formula (3) include, for example,

1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane and the like.

In the formula (4), R ¹ is preferably a hydrogen atom, and R ² , R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms.

Specific examples of the compound represented by the general formula (4) include, for example,

4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol.

In the formula (5), R ¹ is preferably a hydrogen atom, and R ² , R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms.

Specific examples of the compound represented by the general formula (5) include, for example,

1- [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1- [1- Methylethyl] -4-methylethyl} -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -Dihydroxyphenyl) -1-methylethyl) benzene, and the like.

Specific examples of the phenolic compound having the plagiarone skeleton include, for example,

(2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2,4,4-trimethyl-7,2 ' Trihydroxyflavone, and the like.

Specific examples of the phenolic compounds having a spirobi-indane skeleton include 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane-5,6,7,5' 6 ', 7'-hexanol, and the like.

Specific examples of the phenolic compound having a spirobindene skeleton include 3,3'-dimethyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'- Hexanol, and the like.

Of these compounds, (polyhydroxy) benzophenones, the compounds represented by the formula (4) and the compounds represented by the phenolic compounds having a platelet skeleton are preferable, and 2,3,4-trihydroxybenzophenone, 2 , 3,4,4'-tetrahydroxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone, 4,4' - [1- [4- [1- [4- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, Particularly preferred.

In the present invention, the content of the component (E) is preferably from 0.1 to 10 parts by weight, more preferably from 1 to 5 parts by weight, and particularly preferably from 1 to 3 parts by weight, per 100 parts by weight of the alkali- Parts by weight. In this case, if the content of the component (E) is less than 0.1 part by weight, there is a possibility that a desired effect may not be obtained. On the other hand, if it exceeds 10 parts by weight, the formed pattern tends to be easily removed from the substrate during development.

-additive-

The radiation sensitive composition of the present invention contains the above components (A) to (E), but may further contain other additives as required.

Examples of the other additives include fillers such as glass and alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as nonionic surface active agents, cationic surface active agents, and anionic surface active agents; Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like Adhesion promoters; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; And alkali solubility improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

menstruum

The radiation-sensitive composition for forming a coloring layer of the present invention contains the above components (A) to (E) as essential components and contains the above-described additive components as required, but is usually prepared as a liquid composition by blending a solvent.

The solvent may be appropriately selected and used as long as the components (A) to (E) constituting the radiation-sensitive composition and the additive components are dispersed or dissolved and reacted with these components and have appropriate volatility.

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- -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- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

Ethylene glycol monomethyl ether acetate, 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, 3-methoxybutyl acetate (Poly) alkylene glycol monoalkyl ether acetates;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, acetic acid n Propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvic acid n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, Propyl acetate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Among these solvents, from the viewpoints of solubility, pigment dispersibility and coating properties, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate , Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyrate n -Butyl, ethyl pyruvate and the like are preferable.

These solvents may be used alone or in combination of two or more.

The solvent may also be used in combination with a solvent such as benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, A high boiling solvent such as diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate may be used in combination.

These high boiling point solvents may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, but from the viewpoints of coating properties and stability of the resulting radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is preferably 5 to 50% by weight, By weight to 40% by weight.

Color filter

The color filter of the present invention comprises a colored layer formed of the radiation sensitive composition for forming a colored layer of the present invention.

Hereinafter, a method of forming the color filter of the present invention will be described.

First, a light-shielding layer is formed on the surface of a substrate so as to divide a portion where a pixel is formed if necessary, and a liquid composition of a radiation sensitive composition in which a red pigment is dispersed, for example, , And prebaking is performed to evaporate the solvent to form a coating film. Subsequently, the coating film is exposed through a photomask, developed using an alkali developing solution, and the unexposed portion of the coating film is dissolved and removed, followed by post-baking, thereby forming a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

Thereafter, the liquid composition of each of the radiation sensitive compositions in which the green or blue pigment is dispersed is used, and each liquid composition is applied, prebaked, exposed, developed, and post baked in the same manner as above to form a green pixel array A blue pixel array is sequentially formed on the same substrate to obtain a color filter in which pixel arrays of three primary colors of red, green and blue are arranged on a substrate. 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 using the radiation sensitive composition for forming a coloring layer of the present invention.

Examples of the substrate used for forming the pixel and / or the black matrix include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

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, vapor phase reaction, vacuum deposition or the like, if desired.

When the liquid composition of the radiation sensitive composition is applied to a substrate, a suitable coating method such as a spraying method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method, a bar coating method or an ink jet method can be employed , In particular, a spin coating method and a slit die coating method are preferable.

The coating thickness is usually 0.1 to 10 占 퐉, preferably 0.2 to 8.0 占 퐉, and particularly preferably 0.2 to 6.0 占 퐉, as a film thickness after drying.

As the radiation used for forming the pixel and / or the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable Do.

The exposure dose of the radiation is preferably 10 to 10,000 J / m &lt; 2 &gt;.

Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7- -Diazabicyclo- [4.3.0] -5-nonene and the like are preferable.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. may be added in an appropriate amount to the alkali developing solution. After the alkali development, it is usually washed with water.

As the development processing method, a shower development method, a spray development method, a deep (immersion) development method, a puddle development method, or the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

The color filter of the present invention thus obtained is very useful for high-precision fine color liquid crystal display elements, color image pickup tube elements, color sensors 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.

As one embodiment of the color liquid crystal display element of the present invention, a radiation sensitive composition for forming a coloring layer of the present invention is used to form a pixel and / or a black matrix on a thin film transistor substrate array as described above It is possible to manufacture a color liquid crystal display element with high precision and fineness.

&Lt; Example 1 >

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

Mw and Mn of the resins obtained in the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.

Device: GPC-101 (manufactured by Showa Denko K.K.).

Columns: 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 alkali-soluble resin

Synthesis Example 1

A cooling tube and a stirrer, 3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Then, 20 parts by weight of methacrylic acid, 20 parts by weight of N-phenylmaleimide 30 parts by weight of benzyl methacrylate, 20 parts by weight of styrene, and 5 parts by weight of? -Methylstyrene dimer as a chain transfer agent as a molecular weight control agent were purged with nitrogen, and the reaction solution was stirred at 80 ° C The temperature was raised, and polymerization was carried out at this temperature for 3 hours. And 0.5 part by weight of 2,2'-azobisisobutyronitrile were further added, and further polymerization was carried out for 1 hour. Thereafter, the temperature was raised to 100 ° C. and polymerization was continued for 1 hour to obtain a resin solution (solid concentration = 33.0% by weight) &Lt; / RTI &gt; The resin thus obtained had Mw = 9,500 and (Mw / Mn) = 2.0. This resin is referred to as "resin (B-1) &quot;.

Synthesis Example 2

A cooling tube and a stirrer, 4 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Then, 15 parts by weight of methacrylic acid, 15 parts by weight of N-phenylmaleimide 20 parts by weight of benzyl methacrylate, 35 parts by weight of benzyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of glycerol monomethacrylate, 10 parts by weight of ω-carboxypolycaprolactone monoacrylate and δ-methylstyrene as a chain transfer agent as a molecular weight control agent And 6 parts by weight of the mixture were purged with nitrogen, and the temperature of the reaction solution was raised to 80 DEG C while gently stirring, and the mixture was polymerized for 3 hours while maintaining the temperature. And 0.5 part by weight of 2,2'-azobisisobutyronitrile were further added, and further polymerization was carried out for 1 hour. Thereafter, the temperature was raised to 100 ° C. and polymerization was continued for 1 hour to obtain a resin solution (solid concentration = 33.0% by weight) &Lt; / RTI &gt; The resin thus obtained had Mw = 7,500 and (Mw / Mn) = 2.1. This resin is referred to as "resin (B-2) &quot;.

Synthesis Example 3

A cooling tube and a stirrer, 3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Then, 15 parts by weight of methacrylic acid, 30 parts by weight of acenaphthylene 40 parts by weight of benzyl methacrylate, 10 parts by weight of glycerol monomethacrylate, 5 parts by weight of? -Carboxylic polycaprolactone monoacrylate, and 5 parts by weight of? -Methylstyrene dimer as a chain transfer agent as a molecular weight control agent, After purging with nitrogen, the temperature of the reaction solution was raised to 80 캜 while gently stirring, and polymerization was carried out at this temperature for 3 hours. And 0.5 part by weight of 2,2'-azobisisobutyronitrile were further added, and further polymerization was carried out for 1 hour. Thereafter, the temperature was raised to 100 ° C. and polymerization was continued for 1 hour to obtain a resin solution (solid concentration = 33.0% by weight) &Lt; / RTI &gt; The resin thus obtained had Mw = 11,000 and (Mw / Mn) = 2.2. This resin is referred to as "resin (B-3) &quot;.

Synthesis Example 4

A cooling tube and a stirrer, 3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Then, 15 parts by weight of methacrylic acid, 15 parts by weight of N-phenylmaleimide 25 parts by weight of benzyl methacrylate, 15 parts by weight of styrene, 10 parts by weight of glycerol monomethacrylate, 10 parts by weight of? -Carboxylic polycaprolactone monoacrylate and? -Methylstyrene as a chain transfer agent as a molecular weight control agent And the mixture was purged with nitrogen. The temperature of the reaction solution was raised to 80 캜 while gently stirring, and the mixture was polymerized at this temperature for 3 hours. And 0.5 part by weight of 2,2'-azobisisobutyronitrile were further added, and further polymerization was carried out for 1 hour. Thereafter, the temperature was raised to 100 ° C. and polymerization was continued for 1 hour to obtain a resin solution (solid concentration = 33.0% by weight) &Lt; / RTI &gt; The resin thus obtained had Mw = 10,000 and (Mw / Mn) = 2.2. This resin is referred to as "resin (B-4) &quot;.

Synthesis Example 5

A cooling tube and a stirrer, 4 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monoethyl ether were charged. Then, 15 parts by weight of methacrylic acid, 30 parts by weight of acenaphthylene 35 parts by weight of benzyl methacrylate, 20 parts by weight of glycerol monomethacrylate, and 6 parts by weight of? -Methylstyrene dimer as a chain transfer agent as a molecular weight control agent were charged and replaced with nitrogen, and the reaction solution was stirred at 80 ° C The temperature was raised, and polymerization was carried out at this temperature for 3 hours. And 0.5 part by weight of 2,2'-azobisisobutyronitrile were further added, and further polymerization was carried out for 1 hour. Thereafter, the temperature was raised to 100 ° C. and polymerization was continued for 1 hour to obtain a resin solution (solid concentration = 33.0% by weight) &Lt; / RTI &gt; The resin thus obtained had Mw = 12,000 and (Mw / Mn) = 2.2. This resin is referred to as "resin (B-5) &quot;.

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 40 parts by weight of p-vinylbenzyl glycidyl ether, 27 parts by weight of N-phenylmaleimide, 17 parts by weight of styrene and 16 parts by weight of benzyl methacrylate were mixed with 300 parts by weight of propylene glycol monomethyl ether acetate , 4 parts by weight of 2,2'-azobisisobutyronitrile and 6 parts by weight of? -Methylstyrene dimer were further added, followed by nitrogen purging for 15 minutes. After purging with nitrogen, the reaction vessel was heated to 80 캜 with stirring and reacted for 5 hours to obtain a resin solution containing 25% by weight of styrene epoxy resin. The styrene epoxy resin had Mw = 6,000 and (Mw / Mn) = 2.5.

200 parts by weight of a resin solution containing the obtained styrene epoxy resin, 10 parts by weight of methacrylic acid as an unsaturated monocarboxylic acid (X), 0.2 parts by weight of p-methoxyphenol, 0.2 parts by weight of tetrabutylammonium bromide, And 300 parts by weight of ether acetate were put into a flask and reacted at a temperature of 120 DEG C for 9 hours. Thus, one equivalent of methacrylic acid reacted with one equivalent of the epoxy group of the styrene epoxy resin. Further, 16 parts by weight of 4-cyclohexene-1,2-dicarboxylic acid anhydride as the polybasic acid anhydride (y) was added and reacted at 80 DEG C for 6 hours. The reaction mixture was rinsed twice with maintaining the liquid temperature at 80 占 폚 and concentrated under reduced pressure to obtain a resin solution containing 20% by weight of the alkali-soluble resin. The resin thus obtained had Mw = 7,800 and (Mw / Mn) = 2.6. This resin is referred to as "resin (B-6) ".

Preparation of pigment dispersion

Production Example 1

(A) as a colorant; Pigment Red 254 / C.I. 15 parts by weight of Pigment Red 177 = 80/20 (by weight) mixture, 4 parts by weight (in terms of solid content) of Disperby-2001 as a dispersing agent and 6 parts by weight of (B-1) And 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to prepare a pigment dispersion (r).

Production Example 2

(A) as a colorant; Pigment Green 36 / C.I. Pigment Yellow 138 / C.I. 15 parts by weight of Pigment Yellow 150 = 50/40/10 (weight ratio), 4 parts by weight (in terms of solid content) of Dispersible-2001 as a dispersing agent and 5 parts by weight (B-2) as an alkali- 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 prepare a pigment dispersion (g).

Production Example 3

(A) as a colorant; Pigment Blue 15: 6 / C.I. 15 parts by weight of Pigment Violet 23 = 95/5 (weight ratio), 4 parts by weight (in terms of solid content) of Dispersible-2001 as dispersing agent and 5 parts by weight (B-2) as alkali- ) 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 prepare a pigment dispersion (b).

Production Example 4

20 parts by weight of carbon black (manufactured by Mikuni Shuzo Co., Ltd.) as a colorant, 2 parts by weight (in terms of solid content) of Disperby-2001 as a dispersing agent, and 4 parts by weight of (B) (In terms of solid content) 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 (bk1).

Production Example 5

20 parts by weight of Disorbic-167 as a dispersing agent (in terms of solid content), (B) 3 parts by weight of (B-3) as an alkali-soluble resin, (A) 20 parts by weight of carbon black (manufactured by Mikuni Shikiso Co., (In terms of solid content) and 75 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 (bk2).

Example 1

Preparation of liquid composition

8 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer (C), (D) 100 parts by weight of the pigment dispersion (r), (B) 6 parts by weight of the resin (B-4) as the alkali- ) 3 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 0.15 parts by weight of 4,4 '- [1- [4- [1- [4- hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 150 parts by weight of ethyl 3-ethoxypropionate as a solvent, And 25 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a liquid composition (R1) for forming a colored layer.

The liquid composition R1 was evaluated according to the following procedure. The evaluation results are shown in Table 2 below.

Formation of patterns

The liquid composition R1 was coated on the surface of a glass substrate using a spin coater and prebaked at 90 캜 for 2 minutes to form a coating film having a thickness of 2.5 탆. Thereafter, the substrate was cooled to room temperature, and a high-pressure mercury lamp was used as a coating film on the substrate, and the exposure gap was set to 200 mu m through a photomask and exposed at an exposure amount of 1,000 J / m &lt; 2 &gt;. Thereafter, a shower phenomenon was carried out for 50 seconds by discharging a 0.04 wt% aqueous solution of potassium hydroxide of 23 DEG C at a developing pressure of 2 kgf / cm &lt; 2 &gt; (nozzle diameter of 1 mm) to the coating film on the substrate and then post baking at 230 DEG C for 30 minutes Thereby forming a pixel array in which red line-and-space (L / S) patterns are arranged on the substrate.

evaluation

When the pixel array on the substrate was observed with an optical microscope, no defects were found at the edge of the pixel pattern. Further, when the cross section of the pixel pattern on the substrate was observed with a scanning electron microscope (SEM), no undercut was found. The line width of the pixel pattern formed through the photomask having a slit width of 90 탆 was measured by an optical microscope and found to be 93.0 탆.

Examples 2 to 17 and Comparative Examples 1 to 6

The liquid compositions (R2) to (R3), (G1) to (G3), and (G3) were obtained in the same manner as in Example 1 except that the kind and amount of the constituent components in Example 1 were changed as shown in Table 2 B1) to (B3) and (BK1) to (BK14).

Subsequently, except that the liquid compositions (R2) to (R3), (G1) to (G3), (B1) to (B3) and (BK1) to (BK14) were used instead of the liquid composition 1 were evaluated in the same manner. The results are shown in Table 2.

In Table 1, the respective components are as follows.

C-1: dipentaerythritol hexaacrylate

C-2: Tris (2-hydroxyethyl) isocyanurate triacrylate (trade name: M-315, manufactured by Toagosei Co., Ltd.)

D-1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369, Ciba Specialty Chemicals)

D-2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (Irgacure 907, Ciba Specialty Chemicals)

D-3: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- acetyloxime) (trade name Irgacure OX02, Manufactured by Specialty Chemicals)

E-1: 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene] bisphenol

E-2: 2,3,4-trihydroxybenzophenone

E-3: 2,3,4,4'-tetrahydroxybenzophenone

E-4: 2-Methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-

E-5: 2,3,4,2 ', 6'-Pentahydroxybenzophenone

F-1: Malonic acid

F-2: Nonionic surfactant (trade name: A-60, manufactured by Kao Corporation)

F-3: Polymerization inhibitor phenothiazine

EEP: ethyl 3-ethoxypropionate

PGMEA: Propylene glycol monomethyl ether acetate

MBA: 3-methoxybutylacetate

&Lt; Industrial Availability >

The radiation-sensitive composition containing the component (E) of the present invention is excellent in adhesion with the substrate even when the content of the coloring agent contained in the radiation-sensitive composition is high, and has high precision and fine pattern shape, A pixel and a black matrix in which the pattern line width is not thick can be formed.

Accordingly, the radiation sensitive composition of the present invention can be very suitably used for the production of various color filters including color filters for color liquid crystal display devices and color separation color filters for solid-state image pickup devices in the field of electronics.

Claims (7)

(A) a colorant, (B) an alkali-soluble resin, (C) a monomer having at least two radically polymerizable unsaturated bonds, (D) at least one compound selected from the group consisting of an acetophenone compound and an O- (E) a compound represented by the following formula (4), and the content of the component (E) is 0.1 to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin (B) By weight based on the total weight of the composition. &Lt; Formula 4 >

[In the formula 4, R ¹ represents a group the same as R ¹ of formula 1, R ^2, R ³ and R ⁴ each represent the same group with the general formula (I) of R ^2, R ³ and R ⁴ of formula 2, m, p + q? 5, r + s? 5, t + u? 4, n + q + s + u where n, p, q, r, s, t and u are integers of 0 or more. 1 &gt; The resin composition according to claim 1, wherein the alkali-soluble resin (B) is at least one selected from the group consisting of a colorant containing at least one selected from the group consisting of a polymer having a repeating unit represented by the following formula (6) and a polymer having a repeating unit represented by the following formula Sensitive layer composition. (6)

(Wherein R ⁵ represents a hydrogen atom or a methyl group) &Lt; Formula 7 >

(Wherein R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X is a monovalent organic group having an acryloyl group or a methacryloyl group, a vinyl group or a 1- Methyl vinyl group, Y represents a divalent organic group, and h represents an integer of 1 to 5) The positive resist composition according to claim 2, wherein the alkali-soluble resin (B) further contains a polymer having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (8) and a repeating unit represented by the following formula A radiation-sensitive composition for forming a colored layer. (8)

(Wherein R ⁹ represents a straight, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms) &Lt; Formula 9 >

(Wherein R ¹⁰ to R ¹⁵ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group) The radiation sensitive composition for forming a coloring layer according to claim 1, wherein (A) the content of the coloring agent is 30 to 60% by weight of the total solid content. A color filter having a colored layer formed by using the radiation sensitive composition for forming a colored layer according to claim 1. A color liquid crystal display device comprising the color filter according to claim 5. delete