TW201122724A - Color curable composition, color pattern, color filter, method of producing color filter, and liquid crystal display element. - Google Patents

Abstract

This invention provides a color curable composition of a color film capable of inhibiting deterioration of planar characteristics caused by coating and having fewer defects, production method of a color pattern, a color filter, a method of producing the color filter, and a liquid crystal display element by using the color curable composition to provide desirable planar characteristics and fewer defects. The color curable composition comprises: (A) a color agent, (B) a photopolymerizable compound; (C) a photopolymerization initiator, and (D) a copolymer with weight average molecular weight ranging from 1000 to 10000 and having repeated units A0 and B represented by formula (1) below. In formula (1), R1 and R2 represent hydrogen atom or methyl, R0 represents alkylene with 1 to 4 carbons, L represents alkylene with 3 to 6 total carbons, p and q represent the mass percentage of the polymerization ratio of the repeated units, r represents an integer between 1 to 18, and n represents an integer between 1 to 10.

Description

201122724 VI. Technical Field of the Invention: The present invention relates to a coloring curable composition, a color pattern, a color filter (c〇l〇r filter), a method of manufacturing a color filter, and Liquid crystal display element. [Prior Art] A color filter constituting a liquid crystal display (LCD), a color charge coupled device (CCD), or the like is manufactured by photolithography or the like including the following steps: in an organic pigment, A solvent-dispersed composition of a colorant such as an inorganic pigment is added with a binder resin and/or a monomer, a photopolymerization initiator, and other components to form a colored photosensitive composition, which is coated and dried on a transparent substrate. And a coating film having a thickness of about 1 to 3 μm was formed. The coating method on the substrate includes a spin coating method, a die coating method, and the like, and is suitably used according to the characteristics thereof. The spin coating method is widely used for forming a thin film on a substrate having a small size, and the coating liquid is dripped at a central portion of the transparent substrate while rotating the transparent substrate at a constant number of rotations, and the coating liquid is thinned and extended by centrifugal force. A method of applying a coating film having a desired film thickness on the surface of a transparent substrate by controlling the number of rotations, the rotation time, and the like of the transparent substrate suitable for the coating liquid. However, the principle of thinning and spreading the coating film by the centrifugal force of the rotation causes a disadvantage that the coating film thickness of the central portion and the peripheral portion of the transparent substrate becomes too thick compared with the intermediate portion. Further, the die coating method is suitable for forming a film on a large-sized substrate. -4-201122724. The coating liquid is discharged from a slit, and a desired film thickness is formed on the surface of the transparent substrate while moving the slit. The coating method of the coating film. However, in the mechanism, there is a tendency to cause streaky unevenness (strip unevenness) in the vertical direction with respect to the direction in which the slit is made, and the peripheral portion of the coating film is convex, and the film thickness is thinner than the center portion of the substrate. The disadvantage of becoming too thick. Further, there is a problem that a pin hole (white peeling) which is not caused by the drying property of the coating liquid or the surface tension is not caused by the coating method. In particular, in the case of drying under reduced pressure, there are problems such as uneven drying due to unevenness in evaporation or surface depression defects during drying. To solve the problem of unevenness of the coating film in the spin coating method and the die coating method, various attempts have been made so far. For example, Japanese Patent Laid-Open Publication No. 2007-10992 discloses a technique for solving a problem by adjusting the contact angle of a composition. A fluorine-based surfactant is suitably used. Further, a technique for solving the problem by using a composition having a polyoxyalkylene as an antistatic agent is disclosed. Further, in order to solve the problem of coating film unevenness in the spin coating method and the die coating method, various attempts have been made for the surfactant. For example, Japanese Laid-Open Patent Publication No. 2003-322716, JP-A-2003-330174, JP-A-2004-85773, JP-A-2004-126549, JP-A-2004-318111, The technique of controlling the amount of addition of the surfactant in the coloring composition, or the surface tension, contact angle, viscosity, and defoaming property of the coloring composition, respectively, are disclosed in Japanese Laid-Open Patent Publication No. Hei. The same surfactant is used to optimize the surfactant. 201122724 However, for example, the fluorine-based surfactant rapidly segregates on the surface of the coating film at the time of coating, thereby lowering the surface energy of the film, and although controlling the uniformity and drying property of the surface of the coating film, the coloring curable composition is colored. In view of the fact, the compatibility of the fluorine-based surfactant is low, and there is a possibility that the surfactant is separated on the surface of the coating film to cause a sea-island structure, and sufficient performance cannot be obtained. Further, when the molecular weight of the fluorine-based surfactant is large, the surface of the fluorine-based surfactant cannot be segregated rapidly and at a high density, and the drying property of the coating film at the time of coating or under reduced pressure drying cannot be sufficiently controlled. • Moreover, the low surface energy interface after coating is oppositely caused by coating shrinkage or white defects at the time of secondary color coating. Therefore, it is preferred to use the surfactant in the exposure, development, and post-baking steps of the previous step. Stripped or broken down to some extent. The surfactant is a surfactant which contains an unsaturated group such as an acrylonitrile group in the molecule, as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2007-269978. However, such defects are caused by the peeling or the difficulty of the above-mentioned defects. Disclosure of the Invention Problems to be Solved by the Invention The present invention has been made in view of the above background art, and the object of the present invention is as follows. An object of the present invention is to provide a color-curable composition capable of suppressing surface deterioration due to coating and forming a coloring film having few defects. Further, another object of the present invention is to provide a coloring pattern having a good surface shape and a small number of defects, which is obtained by using the coloring curable composition, a color filter having the coloring pattern 201122724, a method for producing the color filter, and a method for producing the color filter. The means for solving the problem of the liquid crystal display element having the color filter is as follows. <1> - a color-curable composition containing (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a formula (1) a repeating unit AG and a repeating unit B, and a polystyrene-equivalent copolymer having a weight average molecular weight of 1,000 or more and 1,000,000 or less as measured by gel permeation chromatography.

R tCH2~ci-p

. Eight O—R〇—(CF2)nF

Repeating unit B repeating unit A0 In the formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group; RQ represents an alkylene group having a carbon number of 1 or more and 4 or less; and L represents a total carbon number of 3 or more. And an alkyl group of 6 or less; R3 represents a hydrogen atom or an alkyl group having a carbon number of 1 or more and 4 or less; P is a mass percentage representing a polymerization ratio of the repeating unit AQ, and p represents 1% by mass or more and 80% by mass. % is a number below 値; q is a mass percentage representing a polymerization ratio of the repeating unit B, and q represents a mass number of 20% by mass or more and 90% by mass of 201122724%; r represents an integer of 1 or more and 1 8 or less; η represents An integer of 1 or more and 10 or less. <2> The colored hardening composition as described in <1> wherein the repeating unit AG in the general formula (1) is the following repeating unit A: R1 I , —Q---

P

/\^(CF2)nF

Repeating unit A In the repeating unit A, Ri represents a hydrogen atom or a methyl group; p is a mass percentage representing a polymerization ratio of the repeating unit A, and represents a number 値 of 1% by mass or more and 8% by mass or less; η represents 1 The above and the following integers. &lt;3&gt; The colored hardening composition according to <1> or <2>, wherein L in the repeating unit 系 is an alkyl group represented by the following formula (2) or formula (3) : 201122724 R-

HG 2 ΗC 2.) /|\

κ2G 4 Ηηκ—C (3) In the general formula (2) and the general formula (3), R4 represents an alkyl group having a carbon number of 1 or more and 4 or less. &lt;4&gt; The colored hardening composition as described in <3> Wherein the R4 is an ethyl group. The color-hardening composition according to any one of the above-mentioned items, wherein the weight average molecular weight of the (D) copolymer is 1,500 or more and 5,000 or less. The colored curable composition according to any one of <1>, wherein P represents 20% by mass or more and 60% by mass. /. The following numbers q and q represent 40% by mass or more and 80% by mass or less. <7> The coloring-curable composition as described in any one of <1>, wherein r is 6 or more and 丨8 or less. <8> The colored curable composition as described in any one of <1> to <7>, wherein the copolymer contains 10% by mass or more and 80% based on the total mass of the copolymer. The repeating unit AQ′ of the mass% or less and the repeating unit 201122724 &lt;9&gt; as in &lt;1&gt;~&lt;8&gt; containing 20% by mass or more and 90% by mass or less based on the total mass of the copolymer The colored hardening composition of any one of the present invention, wherein the content of the copolymer in the colored curable composition is from 0. 005% by mass to 5% by mass. &lt;10&gt; - A coloring pattern formed by a coloring curable composition as described in any one of &lt;1&gt; to &lt;9&gt;. &lt;11&gt; A color filter comprising a colored pattern as described in &lt;1&gt; on the substrate. &lt;12&gt; - A method of producing a color filter, which is coated on a substrate by a spin coating method, a slit and a spin method, or a die coating method, such as &lt;1&gt;~&lt;9&gt; a coloring layer forming step of the coloring composition of the coloring composition; and a coloring pattern forming step of exposing the formed coloring layer to a pattern and developing to form a colored pattern. &lt;13&gt; A liquid crystal display element using a color filter as described in &lt;11&gt;. According to the present invention, it is possible to provide a color-curable composition capable of suppressing surface deterioration due to coating and forming a coloring film having few defects. Further, according to the present invention, it is possible to provide a color pattern having a small planar shape and having few defects, a color filter having the colored pattern, a method for producing the color filter, and a method for using the colored curable composition. A liquid crystal display element of the color filter. [Embodiment] -10- 201122724 Mode for Carrying Out the Invention Hereinafter, the present invention will be described in detail. Colored hardening composition

The color hardening composition of the present invention contains (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a repeating unit represented by the following formula (1) AG and repeating unit B, and the polystyrene-converted copolymer having a weight average molecular weight of 1,000 or more and 10,000 or less as measured by gel permeation chromatography" R1 - CH2 - c - L p

〇人O —R0—(CF2)nF

Repeating unit A0 repeating unit B (In the general formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group, and RG represents an alkylene group having a carbon number of 1 or more and 4 or less. L represents a total carbon number of 3 Above and below 6 alkylene groups, P represents the mass percentage of the polymerization ratio of the repeating unit A11, P represents the mass percentage of 1 〇 mass% or more and 80% by mass or less; q represents the mass percentage of the polymerization ratio of the repeating unit B, q represents a number 20 of 20% by mass or more and 90% by mass or less. r represents an integer of 1 or more and 18 or less, and η represents an integer of 1 or more and 10 or less.) The present inventors intend to solve the spin coating method and the die coating method. In the problem of coating film non-uniformity, focusing on surfactants and conducting drill collars, 'Jun-11-201122724, found that in the precise coating control, in the molecular design of the necessary surfactant, the structure of the compatible group With the importance of molecular weight, the present invention has been completed. In the colored curable composition of the present invention, the surface tension of the colored curable composition is lowered by containing the components (A) to (D), and the wettability of the coated surface of the substrate or the like is increased without white peeling. Defects. Further, by the effect of the extremely high uneven distribution of the component (D) on the surface (biasing effect), the drying of the coating step can be homogenized, and the unevenness of the unevenness due to uneven drying can be greatly reduced. . It is considered that this high surface bias is effective because the weight average molecular weight of the component (D) is 1,000 or more and 1,000,000 or less, whereby the high-density alignment can be achieved, and the component (D) contains a repeating unit having a branched alkyl group. Thereby, it is possible to have a moderate degree of hydrophobicity. Hereinafter, each component of (A) to (D) will be described in detail. (D) copolymer containing a repeating unit represented by the formula (1): a repeating unit represented by the formula (1) and a repeating unit B. The colored hardening composition of the present invention contains (D) a formula containing the following formula ( 1) A repeating unit and a repeating unit B represented by the copolymer, and a polystyrene-equivalent copolymer having a weight average molecular weight of 1,000 or more and 10,000 or less as measured by gel permeation chromatography. Hereinafter, the copolymer is appropriately referred to as "specific copolymer". Further, the specific copolymer functions as a fluorine-based surfactant in the colored curable composition of the present invention. Therefore, it is also referred to as "a specific fluorine-based surfactant" in the present specification. -12- 201122724

Repeating unit B repeating unit A0 In the above formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group, and RQ represents an alkylene group having a carbon number of 1 or more and 4 or less. L represents a total carbon number of 3 The above alkyl group is 6 or less, and r3 represents a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms. P is a mass percentage representing a polymerization ratio of the repeating unit A &lt;), and p represents a number 値 of 10% by mass or more and 80% by mass or less; q is a mass percentage representing a polymerization ratio of the repeating unit B, and q represents 20% by mass The above and 90% by mass or less. r represents an integer of 1 or more and 18 or less; n represents an integer of 1 or more and 1〇 or less. Further, the total carbon number of L in the above repeating unit ,, when L is a branched alkyl group, means Including the total carbon number of the alkyl group which constitutes the branched moiety. The RG may be a linear stretcher base or a branch base, preferably a linear alkyl group. The above L. may be a linear alkylene group, or may be a branched alkyl group, preferably a branched alkyl group, more preferably an alkylene represented by the following formula (2) or formula (3). The genus is preferably a g-alkyl group having a carbon number of 1 or more and 4 or less represented by the following formula (2). In the following general formula, R4' is compatible with the wettability of the surface to be coated on the scale of -13,227,227, and it is preferable that the carbon number is 1 or more, and the alkyl group having 2 or more carbon atoms is more preferable. That is, ethyl is the best. The alkyl group below 3 is a carbon number 2 alkane R4

GH2eH (2) R4 I chgh2 (3) Further, the above repeating unit AQ is preferably the following repeating unit A, that is, Ro is an ethyl group.

CH2-C

P

O' O ^//^CF2) nF Repeating unit A In the above repeating unit A, 'R1 represents a hydrogen atom or a methyl group. p is a mass percentage representing a polymerization ratio of the repeating unit A, and represents a number 値 of 1% by mass or more and 80% by mass or less. n represents an integer of 1 or more and 1〇 or less. The above ρ and q are the mass percentages each representing a polymerization ratio, and ρ represents a number -14 of -14 to 2272724 1 〇 mass% or more and 80 mass% or less. From the viewpoint of the balance of hydrophobicity and hydrophilicity, the mass is 20%. A number of % or more and 60% by mass or less is preferable. Further, q represents a number of 20% by mass or more and 90% by mass or less, and from the viewpoint of the balance of hydrophobicity and hydrophilicity, it is preferably 40% by mass or more and 80% by mass or less. The above r is preferably an integer of 6 or more and 18 or less. Further, it is preferable that n is an integer of 6 or more and 1 〇 or less. The specific copolymer of the present invention may contain a repeating unit A of the repeating unit Α*1 represented by the above formula (1) or a preferred embodiment thereof, and two or more kinds of repeating units. Further, the specific copolymer may contain a repeating unit AQ represented by the above formula (1) and a repeating unit (other repeating unit) other than the repeating unit B. The other repeating unit which the specific copolymer may contain is not particularly limited, and a repeating unit known from an ethylenically unsaturated compound can be suitably used. In all the monomers constituting the repeating unit contained in the specific copolymer, the total of the content of the monomer unit forming the repeating unit aC) and the content of the monomer unit forming the repeating unit B is 90 mol%. the above. In the specific copolymer, the aforementioned repeating unit A is relative to the total mass of the copolymer in terms of the balance of hydrophobicity-hydrophilicity. The content is preferably 10% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 60% by mass or less. Further, in the specific copolymer, from the viewpoint of the balance of hydrophobicity-hydrophilicity, the aforementioned repeating unit B is -15-201122724 2 0% by mass or more and 90% by mass with respect to the total mass of the copolymer. % or less is preferable, and more preferably 40% by mass or more and 80% by mass or less. In the specific copolymer, the total content of the repeating unit Α15 and the repeating unit 代表 represented by the above formula (1) is preferably 60% by mass or more, and preferably 80% by mass or more based on the total mass of the copolymer. For better. The polystyrene-equivalent weight average molecular weight (Mw) of the specific copolymer measured by gel permeation chromatography (GPC) is 1,000 or more and 100,000 or less, and the coating film of the specific copolymer is saved. Preferably, it is preferably 15,000 or more and 8,000 or less, and more preferably 1,500 or more and 5,000 or less. Here, the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography in the present invention is determined by GPC measurement under the following conditions. Use column ·················································································

Flow rate: 0.35 ml/min Temperature: 40 °C Test conditions: RI system: High-speed GPC device type (manufactured by Tosoh: HLC-8220) The following 'exemplified compounds: W-1 to W- 2 4 as: specific copolymerization Specific examples of the invention 'The invention is not limited thereto. Further, the exemplified compound: W-1 to W-24 is a copolymer composed of two repeating units represented by the following. The content (% by mass) of each repeating unit is described in the lower unit of the repeating unit-16-201122724. -1

Chl· -ch2-c- 20% by mass W-2 ch3 Ή2_C- 20 质% W-3 ch3 -ch2-c 0, 〇 \ ^ 20%% CH -[όη2~ο (cf2)6f

CH3 -ch2ch- 80 texture % o- -CH*

Mw: 1500 _3 1c—c_ 2 Ηc (e, F 6 ,0

Mw: 1500

^(CF2)6F c——c • 2 Η.c H3 Η ο Η 80 texture % CH3 -ch2-c-

Mw: 1500 ch2ch3 -ch2ch - o 80% by mass

-H -17- 201122724 W-4 gh3 -ch2-c- CH ~[·〇Η2~0— (C“2) 6 F 20%%

(CH2)2CH3 •ch2ch—o- 80% by mass

-H

Mw: 1500 W-5 ch3 -ch2-c- ch3 I -ch2-c-

/-X^/(CF2)6F 20% by mass

Mw: 1500 (CH2)3CH3 -ch2ch - 〇 - 80% by mass

H W a 6 ch3 -ch2-c 〉人〇 6F 60% by mass ch3 -ch2-c- o

Mw: 1500 ch2ch3 ch2ch——o 40% by mass -CH3 -18- 201122724 W—7 CH,

CH2-C,. ^\^/(CF2&gt;6F 80% by mass -|ch2-

O CH, c-

Ch2ch3 -ch2ch - o- 20% by mass Ή

Mw: 1500 W-8 CH3 CHj-C—o person 〇 ^\/(CF2)6F 1 0% by mass ch3 I ;h2-c-

Mw: 1500. ch2ch3 -ch2ch - 〇 - 90% by mass

-H 12 W-9 CH- ch2-c o person 8f f2) (c CIC — - 2 H c H3 , o 3 0 H 2C Η H c——c 2 H c

H 2 0% by mass ο 8

MW o o o -19- 201122724 W a 10 CH, -ch2-c, 〇々\/(CF2)8F 2 0% by mass W-11 CH, -ch2-c-

Ch3 ~[~CH2-C

Mw: 5000

Ch3 -|~CH2-C (CF2) 1 〇F 2 0% by mass

O

Mw: 10000 ch2ch3 -ch2ch--o S 0 mass% CH2CH3 -ch2ch - o- 8 0 mass%

-H Ή W- 1 2 CH· ;h2-c

Ch3~[-CH2_C, 〇6f 60% by mass

Ch2ch3 -ch2ch - 0 40% by mass

-H

Mw: 1500: -20- 201122724 W—13 CH, CH, -|-CH2—C' /-\^(CF2)6F 20% by mass W-14 CH- -ch2-c -4ch2-c

Mw: 1 500 〇/\^/(CF2)6F 20% by mass W-15 ch3 -|·οη2—c—j—

Ch2ch—〇- 80% by mass ch3 •CH2_G—

Mw: 1500 , /^\^/(CF2)l〇F 20% by mass

-H ch2ch3 OH2CH — 〇 80% by mass CH3 • CH2~C~ One person

Mw: 1500 Ή ch2ch3 I -ch2ch--o- 80% by mass -ch3 -21 - 201122724 W-16 ch3 -ch2-c oS eight 20% lean

(CF2)6F ch3 I -ch2-c-

Mw: 1500 ch2ch3 -ch2ch--o- 80% by mass

-H W-17 CH, GH-

ΌΗ2_C O' '〇/X/\(CF2)6f 20 质% W 18 ch3 -|-ch2—c· -ch2-c

Mw: 1500 ch2ch3 I -ch2ch-o 80 texture % ch3 :h2-c

/^n^CF2)6F 20% by mass • 1500

-H CH2CH3 ch2ch - 〇 80% by mass

-H -22- 201122724 W-1 19 CH, -ch2-c 2 〇质量% W- 2 0

CH

-CH2—C ch3 -ch2-c—

(CF2)6F o C3H5-0 8 0% by mass

Mw: 1000 CH, -ch2-c -CH, (〇f2)6f

—C4H8-O C2H5 2 0% by mass 8 0% by mass 5 0 0 W-2 1 ch3 I ch2-c— CH,

(CF2)6F C5H10-O —C3H7 10 2 0% by mass 8 0% by mass

Mw: 1500 -23- 3 201122724 W-2 2 -ch2-c ?Ηα CH -CH2-C- Ό —

V^\^(CF2)6F -C6H12-〇-C4Hg ho 20%% 80%%

Mw: 1500 W-2 3 CH, -ch2-c

2) gF CH3i -ch2-c- .A,, ch2ch3 OHOH2 - 〇 - H -10 20% by mass 80% by mass

Mw: 1500 W-2 4 CH3 ch3 'CH2—c— ch2-c

,〇/\z\(CF2)6F, 〇 ch2ch31 ch2ch—o Ή 2 3 quality set% 7 7 texture %

Mw: 1500 - 24 - 201122724 The method for producing a specific copolymer is not particularly limited, and a monomer for obtaining a repeating unit represented by the above formula (1) is used, for example, by cationic polymerization using an ethyl group. It is produced by a polymerization method such as cationic polymerization, radical polymerization or anionic polymerization. Among them, the radical polymerization method is particularly preferable because it can be used in general. In the case of producing a specific copolymer in the present invention, in the case of using a radical polymerization method, a polymerization initiator as shown below can be used. As the polymerization initiator, a known compound such as a radical thermal polymerization initiator or a free radical photopolymerization initiator can be used, and a radical thermal polymerization initiator is particularly preferably used. Here, the radical thermal polymerization initiator is a compound which generates a radical by heating to a decomposition temperature or higher. Examples of such a radical thermal polymerization initiator include dimercapto peroxide (acetonitrile peroxide, benzamidine peroxide, etc.) and hydrazine peroxide (methyl ethyl ketone peroxidation). , cyclohexanone peroxide, etc.), hydroperoxide (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxide (di-tert-butyl Peroxide, dicumyl peroxide, dilauryl peroxide, etc.), peroxyesters (tert-butyl peroxyacetate, tert-butylperoxy trimethyl b) An acid ester or the like, an azo compound (such as azobisisobutyronitrile or azobisisovaleronitrile) or a persulfate (ammonium persulfate, sodium persulfate or potassium persulfate). Such a radical thermal polymerization initiator may be used singly or in combination of two or more. Further, the radical polymerization method is not particularly limited, and examples thereof include an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and a solution polymerization method. Solution polymerization for a typical free radical polymerization process is further specified. The other polymerization methods are also similar, and the details are described, for example, in "The Society of Polymer Science" (The Society of Polymer Science, Japan) (Tokyo Kagaku Dojin, 1981). . For the solution polymerization, an organic solvent is used. These organic solvents can be arbitrarily selected within the scope of the object and effect of the present invention. These organic solvents are usually organic compounds having a ruthenium having a boiling point of from 50 ° C to 200 ° C at atmospheric pressure, and it is preferred to uniformly dissolve the organic compounds of the respective constituents. Examples of preferred organic solvents include alcohols such as isopropanol and butanol, ethers such as dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, and dioxane, acetone, and methyl ethyl b. Ketones such as ketones, methyl isobutyl ketone and cyclohexanone, esters of ethyl acetate, butyl acetate, amyl acetate, γ-butyrolactone, aromatics such as benzene, toluene and xylene Hydrocarbons. In addition, these organic solvents may be used alone or in combination of two or more. Further, from the viewpoint of the solubility of the monomer or the produced polymer, a water-mixed organic solvent obtained by using water in the above organic solvent is also suitably used. Further, the solution polymerization conditions are not particularly limited. For example, it is preferred to heat for 1 to 3 hours in a temperature range of 50 ° C to 200 ° C. Further, it is of course required in solution polymerization in such a manner that the generated radicals are not deactivated. It is preferred to carry out inert gas flushing before the start of solution polymerization. Inert gases are generally suitable for use with nitrogen. -26- 201122724 In order to make a specific copolymer within a preferred molecular weight range, a radical polymerization method using a chain transfer agent is particularly effective. As the chain transfer agent, mercaptans can be used (for example, octyl mercaptan, mercapto mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, 18-yard mercaptan, thionine) , p-mercaptothiophenol, etc.), polyhalogenated alkyl (for example, carbon tetrachloride, chloroform, 1,1,1-trichloroethane, 1,1,1-tribromooctane, etc.), low activity Any of the monomer (α-methylstyrene, α-methylstyrene dimer, etc.) is preferably a thiol having 4 to 16 carbon atoms. The amount of such chain transfer agent used has a significant influence depending on the activity of the chain transfer agent, the combination of monomers, polymerization conditions, etc., and must be precisely controlled, usually relative to the total number of moles of the monomers used. 0 · 0 1 mol % ~ 5 0 mol %, preferably 0.0 5 mol % ~ 3 0 mol %, particularly preferably 0.0 8 mol % ~ 2 5 mol %. These chain transfer agents are not particularly limited as long as they are present in the system at the same time as the monomer to be controlled in the polymerization process. It may be added to the monomer or added to the monomer. The specific copolymer preferably has a viscosity at 25 ° C of 200 Pa &gt; s ~ 1 0000 Pa - S. When the specific copolymer has a viscosity at 25 ° C of 200 Pa * s to 10000 Pa • s, a good surface shape can be obtained. The viscosity is preferably from 250 Pa*s to 5000 Pa's, more preferably from 300 Pa-s to 1 000 Pa-s. Further, in the present invention, the "viscosity" of the specific copolymer is a VAR-100 rheometer manufactured by Reologica Instruments AB, and the distance between the gaps is 1.5 mm, the frequency is 1 Hz, the deformation amount is 0.005, and the temperature is raised. The enthalpy measured by the oscillation mode (oscillation -27- 201122724 m 〇de) at a speed of 5 °C / min and in a nitrogen atmosphere. The colored curable composition of the present invention may contain at least one specific copolymer or may contain two or more kinds. Further, as a result of the review, it was surprisingly found that the colored curable composition of the present invention containing the (D) specific copolymer has an effect of better liquid crystal specific resistance in addition to the above effects. The content of the specific copolymer in the color hardening composition of the present invention is preferably from 0.005 mass% to 5 mass%, more preferably from 0.005 mass% to 1 mass%, further preferably from 0.005 mass% to 0.5 mass%. Preferably, 0.01% by mass to 0.2% by mass is optimal. When the content of the (D) specific copolymer is in the above range, excellent coatability can be obtained in the formation of the colored curable composition layer, and a uniform coating film can be formed even when a coating film having a large area is formed. Therefore, when the content of the specific copolymer is within the above range, it is particularly effective when the slit coating is performed by a die coating method or the like on a large substrate. The large substrate referred to herein means a substrate of lmxlm square or more and 5 mx 5 m square or less. The color hardening composition of the present invention may be used together with the (D) specific copolymer to use other surfactants. Examples of the other surfactants include a silicone-based surfactant and a fluorine-based surfactant different from the structure of the specific copolymer (D). As the polyoxo-based surfactant, a surfactant having a siloxane coupling can be listed. Specific examples include Toray Silicone (TORAY SILICONE) DC3PA, same SH7PA, same DC11PA, same SH21PA, -28-201122724 with SH28PA, same 29SHPA, same SH30PA, polyether modified eucalyptus SH8400 (trade name: Toray Silicone (share) ( Dow Corning Toray Co., Ltd.); KP32, KP322, KP323, KP324, KP326, KP340, KP341, KF6001, KF6002, KF6003, X22-160AS (Shin-Etsu Chemical Co., Ltd.) System); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF445 2, TSF4460 (Momentive High Sex Materials)

Performance Materials Inc.)$^)^. Further, examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain which is different from the structure of the (D) specific copolymer. Specific examples thereof include FLUORINERT FC43 0, FLUORINERT FC43 1 (above, Sumitomo 3M (share) (3M)); Megaafac (MEGAFAC) F 1 42D ' Megafac F171' Megafac F172' Megafac F17 3 ' Megafac F177, Megafac F780F, Megafac F781F, Megafac F479, Megafac F4 8 2, Megafac F 5 5 3, Megafac F554, Megafac F486, Megafac F478, Megafac F480, Megafac F484, Megafac F470, Megafac F471, Megafac F483, Megafac F 4 8 9 ' Megafac F487, Megafac F183, Megafac R30 (above, DIC (DIC)); EFTOP EF301, EFTOP EF3 03 ' EFTOP EF351, EFTOP EF352 (above, Mitsubishi Materials Electronics (Stock) Mitsubishi Materials Electronic Chemicals Co., Ltd.); SURFLON S381, SURFLON S 3 82, SURFLON SC1 (H, SURFLON SC105 (above, Asahi Glass Co., -29-201122724)

Ltd.); E5844 (manufactured by Daikin Industries Ltd.); BM-1000, BM-1100 (manufactured by BM Chemie Co., Ltd.), and the like. Further, the other surfactants include a polyfluorene-based surfactant having a fluorine atom, and a polyfluorene-based surfactant having a fluorine atom, and examples thereof include a decane bond and a fluorocarbon chain. Surfactant. Specifically, the product name is Megafac R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (above, DIC). These other surfactants may be used singly or in combination of two or more. (A) Colorant The color hardening composition of the present invention contains (A) a colorant. As the coloring agent, a pigment or a dye can be used. Pigment Examples of the pigment which can be used in the color hardening composition of the present invention include various inorganic pigments or organic pigments which have hitherto been known. Further, in the case where the pigment is preferably an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle diameter as small as possible and a small particle size, and in consideration of handleability, It is preferably a pigment having an average primary particle diameter of 0.0 ΐ μηη to ().3 μιη, more preferably 0.01 μηι to 0·15 μηη. If the particle diameter is within the above range, it contributes to the formation of a color filter having high transmittance, good color characteristics, and high contrast. The average primary particle diameter was observed by SEM (scanning electron -30-201122724 microscope) or TEM (transmission electron microscope), and the average particle size was calculated by measuring the size of 100 particles in a portion where the particles were not aggregated. The inorganic pigment may be a metal compound represented by a metal oxide or a metal salt, and examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, chin, magnesium, chromium, and zinc. 'Metal oxides of ruthenium and the like, and composite oxides of the foregoing metals ο For the above-mentioned organic pigments, for example, CIPig me nt Red l '2, 3, 4, 5, 6, 7, 9, 10, 14 17 , 22, 23, 3 1 ' 38 ^ 4 1 , 48:1' 48:2 , 48:3 , 48:4 , 49 49:1 , 49:2 , 52:1 ' 52: : 2 , .53: 1 ' 5 7:1, 60:1, 63:1, 66, 67, 81:1 ' 8 1:2, 8 1:3, 83 ' 88 ' 90 , 105 , 1 1 2 '119 ' 122, 123 , 144, 146, 149, 150, 155, 166, 168, 169, 170, 17 1 , 172, 175, 176, 177 &gt; 178 ' 179 &gt; 184 ' 185 ' 187 ' 1 8 8 , 190 , 200 , 2 02 ' 206 ' 207 ' 208 ' 209, 210 ' 216, 220, 224, 226, 242, 246 ' 254 ' 25 5 ' 264, 270 ' 272, 279 t CIPig me nt Yello w ] l, 2, 3, 4 ' 5, 6, 1 0, 1 1 , 12 13 , 14 , 1 5 '16' 1 7 , l 8 , 20 24, 3 1' 32, 34, 35, 3 15:1' 36, 36: 1, 37, 37: 1, 40, 42 ' 43 - '53 , 55' 60, 61 « 62 ' 63, 65 ' 73 '74 , 77 ' 8 1 , 83 , 86 , 93 , 94 , 95 , 97 , 98 , 100 , 101 , 104 , 106 ' 108 , 109 , 110 &gt; 113 ' 114 , 115 ' 116 , 117 ' 118 , 119 , 120 , 123 &gt; 125 , 126 , 127 , 128 , -31 - 201122724 , 137 ' 138 , 139 , 147 , 148 , 150 , 15 1 , 152 , 153 , 15 5 , 156 , 161 , 162 , 1 6 4, 166, 167 '168, 169, 17, 1 , 172, 173, 174, 175, 176, 177, 179, 180, '182' 185' 187 '188' 193, 194, 199, 2 13, 214;

129 154 170 18 1 38, 71, 15:6 OH Yes, 150 CIPigmentOrange2, 5, 13, 16, 17:1, 31, 34, 36, 43, 46, 48, 49, 51, 52, 55, 59 , 6〇, 61, 62, 64, 7 3 ; CIPigment. Green 7, 10, 3 g ^ ^ ^ g . CIPigment Blue 1, 2, 15, i5: i, 15: 2, 15: 3, 15 : 4, 16, 22, 60, 64, 66, 79, 79 change the C1 substituent to 80, CIPigment Violet 1, 19^ 23^ 27' 32' 37' 42; CIPigment Brown 25 ' 2 8 ; C. I. P igment B1 ack 1, 7, etc. Among these, the following materials can be preferably used. However, the pigment in the present invention is not limited to this #. CIPigment Yellow 11, 24, i 〇 8, i 〇 9, 110, 138, 139, 151, 154, 167, 180, 185; CIPigment Orange 36, 71; CIPigment Redl 22, 150, 171, 175, 177, 209, 224, 254, 255, 264; CIPigment Violet 19, 23, 32; CIPigment Blue 15:1, 15:3, 15:6, 16' 22' 60' 66; -32- 242 201122724 CIPigment Green 7, 36, 37, 58: CIPigment Black 1, 7. Fineness of the pigment In the present invention, an organic pigment which is finely divided and granulated can be used as needed. The refinement of the pigment is a step of preparing a high-viscosity liquid composition using a pigment, a water-soluble organic solvent and a water-soluble inorganic salt, and grinding the pigment with the liquid composition. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, η·propanol, isobutanol, η-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, and Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, and the like. However, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, sulphur, quinoline, tetrahydrofuran can also be used as long as it can adsorb to the pigment and is not lost to the wastewater. , dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, decane, decane, undecane, dodecane, cyclohexane, methylcyclohexane , halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl hydrazine, and hydrazine _methyl sulphonic acid, etc. . Further, these two or more solvents may be used in combination as needed. In the present invention, the water-soluble inorganic salt may, for example, be sodium chloride, potassium chloride, calcium chloride, barium chloride or sodium sulfate. The water-soluble inorganic salt is used in an amount of 1 times by mass to 5 times the mass of the pigment, and although it has a grinding effect, in terms of productivity, the amount of -33-201122724 is 1 times the mass to 10 times. Further, it is more preferable that the water content of the water-soluble inorganic salt is 1% or less. The amount of the water-soluble organic solvent to be used is in the range of 50% by mass to 300% by mass based on the pigment, preferably in the range of 100% by mass to 200% by mass. After the liquid composition was prepared by the above respective components, the pigment was finely pulverized by a wet pulverizing apparatus. Here, the operating conditions of the wet pulverizing apparatus are not particularly limited, but in order to effectively perform the grinding by the pulverizing medium, in the case where the apparatus is a kneader, the operating condition is preferably the number of rotations of the blades in the apparatus. It is l rpm 〜 00 rpm, and in order to increase the grinding effect, it is preferable that the rotation ratio of the two axes is relatively large. Further, the combination of the operation time and the dry pulverization time is preferably from 1 hour to 8 hours, and the internal temperature of the apparatus is preferably from 50 ° C to 150 ° C. Further, the water-soluble inorganic salt of the pulverizing medium is preferably a pulverized particle size of 5 μm to 50 μm, and has a sharp particle size distribution (i.e., a narrow particle size distribution) and is spherical. Pigment blending (color matching) The organic pigment as a coloring agent can be used alone, but various combinations can be used to improve the color purity. The details of the combination are as follows. For example, as the red pigment, an anthraquinone pigment, an anthraquinone pigment or a diketopyrrolopyrrole pigment may be used alone, and at least one of these may be used together with a disazo yellow pigment or isoporphyrin. It is a yellow pigment or a sulphonone-based yellow pigment, or a mixture of a lanthanide red color pigment, a lanthanide red color pigment or a diketopyrrolopyrrole red color pigment. For example, the ruthenium pigment may be CI Pigment Red 177, and the ruthenium pigment may be CI Pigment Red 155, -34-201122724 CI Pigment Red 224' diketopyrrolopyrrole pigment may be CI Pigment Red 2 5 4 In terms of color reproducibility, it is preferred to mix at least one of them with C. I Pigment Yellow 83, CI Pigment Yellow 139 or CI Pigment Red 177. Further, the mass ratio of the red pigment to the other pigment (red pigment: other pigment) is preferably from 100·5 to 100:80. When it is less than 100:5, it is difficult to suppress the light transmittance of 40 Onm to 50,000 nm, and there is a case where the color purity cannot be improved. Further, if it exceeds 100:80, the coloring power is lowered. The above mass ratio is most suitable for the range of 100:10 to 1 00:65. Further, in the case where the red color pigments are combined with each other, the chromaticity can be adjusted in combination. Further, as the green pigment, a halogenated phthalocyanine pigment may be used alone, or a bisazo yellow pigment, a quinacridone yellow pigment, a methine azo yellow pigment or an isoporphyrin yellow may be used. Mixture of pigments. For example, regarding such an example, at least one of C. I pigment green 7, 3 6, 3 7, 5 8 , with CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Mixing of Pigment Yellow 180 or CI Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment (green pigment: yellow pigment) is preferably 100: 5 to 1 00: 200. When the mass ratio is less than 100:5, it is difficult to suppress the light transmittance of 400 nm to 45 nm and there is a case where the color purity cannot be improved. Further, when the right side exceeds 100:200, the dominant wavelength becomes a longer wavelength, and the target hue of the NTSC (National Television System Committee) is increased. The above-mentioned quality bit is preferably in the range of 100:20 to 100:150. Regarding the blue pigment, the phthalocyanine pigment can be used alone, and it can also be added to -35-201122724 'the mixture of the purple pigment and the second cultivating purple pigment. A particularly suitable example is the mixture of CI Pigment Blue 15:6 and CI Pigment Violet 23. The mass ratio of blue pigment to purple pigment (blue pigment: purple pigment) is 100:0~1 00:1 00. Better, better than 1 00:70. Further, as the pigment suitable for the black matrix use, carbon black, graphite, titanium black 'iron oxide, titanium oxide, or the like may be used alone, and a combination of carbon black and titanium black is preferred. Further, the mass ratio of carbon black to titanium black (carbon black: titanium black) is preferably in the range of 100:0 to 100:60. When the ratio is 100:61 or more, the dispersion stability is lowered. Dye In the present invention, when a dye is used as the (A) coloring agent, a color-curable composition which is uniformly dissolved can be obtained. The dye which can be used as a coloring agent is not particularly limited, and a known dye which is conventionally used for color filter applications can be used. For example, Japanese Laid-Open Patent Publication No. Sho 64-90403, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The specification of U.S. Patent No. 5,667,920, U.S. Patent No. 5, No. 5, No. 5, No. 5, No. 5, Japanese Patent Application Laid-Open No. Hei No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Kaiping No. 1 1 -3 02283 'Japanese Unexamined Japanese Patent Publication No. 7_2 8 6 1 〇7, Japanese Patent No. 36-201122724, Japanese Patent Publication No. 2 - 4723, Japanese Patent Publication No. 8_1 5 5 22, and Sakamoto Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese special open 2〇〇2_ 1422 1st bulletin, Japan special open 2002- 1 4222 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. pigment. In terms of chemical structure, a pyrazole azo system, an aniline azo system, a tribasic keel system, a bismuth system, a bismuth ketone system, a subunit base system, an oxophthalocyanine system, a shame and a triterpenoid can be used. Azo system, pyridone azo, cyanine, morphine, phenanthrene, hydrazine, hydrazine, phthalocyanine, phthalocyanine, benzopyran, indigo A dye such as a dye. Further, depending on the purpose, a dye and the aforementioned pigment may be used in combination as a coloring agent. Pigment Dispersion In the present invention, when a pigment is used as the (tantalum) colorant, it is preferred to prepare the color hardening composition of the present invention by using a pigment dispersion liquid prepared in advance. The content of the pigment in the pigment dispersion liquid is preferably from 10% by mass to 60% by mass, more preferably from 15% by mass to 50% by mass, based on the total solid content (mass) of the composition. When the content of the pigment is within the above range, it is effective in that the color density is sufficient and the color characteristics are excellent. Dispersant -37- 201122724 The pigment dispersion liquid in the present invention is preferably contained in at least one type of dispersant. By containing the dispersant, the dispersibility of the pigment can be improved. As the dispersant, for example, a known pigment dispersant or a surfactant can be suitably used. Specifically, many kinds of compounds can be used, and examples thereof include an organic siloxane polymer ΚΡ 341 (manufactured by Shin-Etsu Chemical Co., Ltd.), a (meth)acryl-based (co) polymer POLYFLOW Ν . . 75. a cationic surfactant such as Νο. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.); Polyoxyethylene ethyl lauryl ether, polyisoethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxyethyl phenyl ether, Non-ionic surfactants such as polyethylene glycol dilaurate, polyethylene glycol distearate, D sorbitan fatty acid ester; W004, W0 0 5, 017 (Yu Shang) Anionic surfactant; etc.; 〖Human-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all are Cibafin Chemical Co., Ltd.), Dispersion Aid (DISPERSE AID) 6, Dispersing Aid 8, Dispersing Aid 15, Dispersion 91 〇〇 (all are manufactured by San Nopco Ltd.) and other polymer dispersants; SOLSPERS 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000 , 28000, etc. Various Soaps Dispersing Agents (The Lubrizol Corporation); ADEKAPLURONIC L31, F38, L42, -38- 201122724 L44, L61, L64 , F68 , L72 , P95 ' F77 , P84 , F87 , P94 , L101 , P103 ' F108 , L121 , P-123 (made by ADEK: A Corporation) and Ian Net (I〇NET) S-20 (manufactured by Sanyo Chemical Industries Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2 1 5 0 (manufactured by B YK Chemie Co., Ltd.). Other examples include oligomers or polymers having a polar group at a molecular terminal or a side chain such as an acrylic copolymer. The content of the dispersant in the pigment dispersion liquid is preferably from 1% by mass to 100% by mass, more preferably from 3% by mass to 70% by mass, based on the mass of the pigment. Pigment Derivative The pigment dispersion of the present invention may optionally contain a pigment derivative. By adsorbing a portion or a polar group-derived pigment derivative having an affinity for a dispersant to the surface of the pigment, and using it as a point of adsorption of the dispersing agent, the pigment can be dispersed as fine particles in the pigment dispersion or colored hardened. 'In the composition' and prevent it from agglomerating again. As a result, the colored curable composition can be suitably used for forming a color filter having high contrast and excellent transparency. Specifically, the "pigment derivative" is a compound obtained by using an organic pigment as a matrix and introducing an acidic group, a basic group, or an aromatic group as a substituent in the side chain. Specific examples of the organic pigment include a quinacridone pigment, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoporphyrin-39-201122724 pigment, and an isoindolinone. Pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzimidazole anthraquinone pigments, and the like. A pale yellow aromatic polycyclic compound such as a naphthalene, a oxime, a diterpene or a quinoline which is not called a dye is usually included. In the case of the pigment derivative, it is described in Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. 2005-234478, Japanese Patent Laid-Open No. Hei. No. Hei. The content of the pigment derivative in the pigment dispersion liquid is preferably from 1% by mass to 30% by mass based on the mass of the pigment, and more preferably from 3% by mass to 20,000% by mass. When the content is within the above range, the viscosity can be lowered and the dispersion can be favorably performed, and the dispersion stability after dispersion can be improved, and the excellent color characteristics of the transmittance can be obtained, and the color filter can be formed. High contrast with good color characteristics. Dispersion method Regarding the dispersion method of the pigment, for example, a mixed pigment and a dispersant may be used, which are previously dispersed by a homogenizer or the like, and then used as a bead disperser using zirconia beads or the like (for example, GETZMANN Co., Ltd.) A method of making a microdispersion by dispersing beads (DISPERMAT) or the like. The dispersion time is suitable for about 3 hours to 6 hours. Further, as described above, when a dye and a pigment are used as a coloring agent, it is possible to use -40-201122724 to use a pigment dispersion liquid and a dye dissolved in a solvent, or to mix a dye with a pigment dispersant. (B) Photopolymerizable Compound The colored curable composition of the present invention contains (B) a photopolymerizable compound. The photopolymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C or higher at normal pressure, wherein the acrylate compound having four or more functional groups is preferably Better. The compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 1 〇〇 ° C or more at normal pressure may, for example, be polyethylene glycol mono(meth)acrylate or polypropylene glycol. Monofunctional acrylates, methacrylates such as mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di(meth) acrylate, trimethylol ethane tri (Meth) acrylate, neopentyl glycol di(meth) acrylate, neopentyl alcohol tri(meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol hexa Methyl) acrylate, hexanediol (meth) acrylate, trimethylolpropane tris(propylene decyloxypropyl) ether, tris(propylene decyloxyethyl) isocyanate, Addition of ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane, and then a (meth)acrylated product, neopentylol or dipentaerythritol. Acrylate-esterified material, Japanese special public Zhao 4 8 -4 1 70 8 , Japanese special public Zhao 50-6034, Japanese special The urethane acrylates described in Japanese Laid-Open Patent Publication No. SHO-48-63183, No. Sho. Reaction of an epoxy resin with (meth)acrylic acid - 41 - 201122724 A polyfunctional acrylate or methacrylate such as an epoxy acrylate of a product. Further, photocurable monomers and oligomers described in the Journal of the Adhesion Society o f J ap an Vo 1.2 0, No. 7, 3 00 to 308 can also be used. Further, a specific example of the general formulae (1) and (2) in JP-A-10-62986 may be used, and the above-described polyfunctional alcohol may be added to ethylene oxide or propylene oxide (A). A compound obtained by acrylated. Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the structure in which these acryl oxime groups are permeable to ethylene glycol or propylene glycol residues are preferred. Such oligomeric forms can also be used. Further, such succinic acid derivatives can also be used. In addition, the urethane acrylates described in Japanese Patent Publication No. Sho 48-41708, JP-A-51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765, Japanese Patent Publication No. Sho. A urethane compound having an ethylene oxide skeleton described in Japanese Patent Publication No. Sho 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-394-18 is also suitable. Further, an addition polymerization having an amine structure or a thioether structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, the disclosure of which is incorporated herein by reference. As the compound, a photopolymerizable compound having a very excellent photospeed can be obtained. Commercially available products include urethane oligomer UAS-l, UAB-140 (Nipp〇n Paper Chemicals -42- 5 201122724), UA-7200 ( Shin-Nakamura Chemical Industry Co., Ltd. (Shin-Nakamura

Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku C ο , L td.), UA - 3 0 6 Η, UA - 3 0 6 T, UA - 3 0 61, AH-600, T-600, AI-600 (manufactured by Kyoei Co., Ltd.). Further, an ethylenically unsaturated compound having an acid group is also suitable, and as the commercially available product, for example, a carboxyl group-containing product manufactured by T〇a Gosei (:〇., 1^.) A functional acrylate butyl group 0_7 5 6 , a carboxyl group-containing 5-functional acrylate ester, TO-1382, TO-23 49, etc. The photopolymerizable compound may be used alone or in combination of two or more. The content of the compound in the colored curable composition is preferably from 5% by mass to 50% by mass based on the total solid content, more preferably from 7% by mass to 40% by mass, and further preferably from 10% by mass to 35% by mass. (C) Photopolymerization initiator The coloring composition of the present invention contains (C) a photopolymerization initiator. The photopolymerization initiator may, for example, be disclosed in Japanese Laid-Open Patent Publication No. Hei 5-7-6096 An active halogen compound such as a halomethyl-s-tripper described in the above-mentioned publications, such as the halomethyl oxadiazole, the Japanese Patent Publication No. 59-1281, and the Japanese Patent Laid-Open Publication No. SHO-53-133 U.S. Patent No. 4 3 1 8 7 9 1 and European Patent Application No. 88〇5〇 An aromatic carbonyl compound such as a ketal, an acetal or a benzoin alkyl ether described in the book, an aromatic ketone compound such as a diphenyl ketone described in the specification of U.S. Patent No. 4,199420, and a French invention patent No. 2 4 5 6 7 4 岫 ( ( 9 9 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二A compound such as a lophine dimer or a bismuth organoboron complex such as JP-A-8-015521. In the case of the photopolymerization initiator, an acetophenone-based, ketal-based or diphenyl ketone is used. Department, the present marriage system, the present methionine system, the ketone ketone system, the triterpenoid system, the halomethyl hydrazine- hydrazine system, the ay steep system, the fragrant sulphate system, the slightly dioxin system, A biimidazole-based, an oxime-based ester-based or the like is preferred. The acetophenone-based photopolymerization initiator is preferably, for example, 2,2-diethoxyacetophenone or p-dimethylaminobenzene. Ethylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4, isopropyl-2_hydroxy-2-methyl-benzene acetone For the ketal-based photopolymerization initiator, for example, benzyldimethylketal, benzyl-β-methoxyethylacetal, etc. are mentioned. About the aforementioned diphenylketone photopolymerization initiator Suitable examples are, for example, diphenyl ketone, 4,4'-(bis-dimethylamino)diphenyl ketone, 4,4, bis(di-diethylamino)diphenyl ketone, 4 , 4 dichlorodiphenyl ketone, _ hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)·butanone-1 , 2-tolyl-2-dimethylamino-i_(4-morpholinylphenyl)-butanone-1 '2-methyl-1-[4-(methylthio)phenyl]-2 Morpholinylacetone-1 and the like. Examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and methyl hydrazine-benzene. Formyl benzoate and the like. With respect to the above-mentioned anthrone-based photopolymerization initiator, for example, di-B-44-201122724-based 9-oxothiolane [Ij singer, diisopropyl 9-oxothiopurine ill comet, monoisopropyl 9 can be suitably used. - Oxygen sulfur U mountain comet, chlorine 9 · oxopurine [lj喔 and so on. With respect to the above-mentioned tritrap-based photopolymerization initiator, for example, 2,4·bis(trichloromethyl)-6-p-methoxyphenyl-s-three tillage and 2,4-bis (three) can be suitably used. Chloromethyl)-6-p-methoxystyryl-s-trin, 2,4-bis(trichloromethyl)-6-(lp-dimethylaminophenyl)-1,3 -butadienyl-s-tripper, 2,4-bis(trichloromethyl)-6-biphenyl-s-trin, 2,4-bis(trichloromethyl)-6-(p -Methylbiphenyl)-s-triterpene, p-hydroxyethoxystyryl-2,6-di(trichloromethyl)-s-trin, methoxystyryl-2,6 - bis(trichloromethyl)-s-tripper, 3,4-dimethoxystyryl-2,6-di(trichloromethyl)-s-trisole, 4·benzooxane Benzoxolane-2,6-bis(trichloromethyl)-s-triterpene, 4-(anthracene-bromo-p-indole, fluorenyl-(diethoxycarbonylamino)-phenyl)- 2,6-bis(chloromethyl)-s-tripper, 4-(p-fluorene, fluorenyl-(diethoxycarbonylamino)-phenyl)-2,6-di(chloromethyl)- S-three tillage and so on. As the halomethyl oxadiazole-based photopolymerization initiator, for example, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole or 2-trichloromethyl- can be suitably mentioned. 5-(cyanostyryl)-1,3,4-oxadiazole '2-trichloromethyl-5-(naphthalene-buyl)-1,3,4-oxadiazole, 2-trichloro Methyl-5-(4-styryl)styryl-1,3,4-oxadiazole and the like. The acridine-based photopolymerization initiator may, for example, be, for example, 9-phenyl acridine or 1,7-bis(9-acridinyl)heptane. With respect to the aforementioned coumarin-based photopolymerization initiator, for example, 3-methyl-5-amino-((s-trimethyl-2-yl)amino)-3-phenylcoumarin can be suitably used. , 3-Chloro 5- 5-45- 201122724 Diethylamino-((S-Triton-2-yl)amino)-3-phenylcoumarin, 3-butyl-5-dimethyl Amino-((s-trit-2-yl)amino)-3-phenylcoumarin and the like. With respect to the above-mentioned singular dimer-based photopolymerization initiator, for example, 2-(anthracene-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2-(anthracene-methoxy) can be suitably used. Phenylphenyl)-4,5-diphenylimidazolyl dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazolyl dimer, and the like. The biimidazole-based photopolymerization initiator may, for example, be 2-nonylbenzimidazole or 2,2'-benzothiazole disulfide. In addition to the above, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, fluorenyl-benzylidene- 4'-(benzofluorenyl)benzene can also be mentioned. Mercapto-hexyl-ketooxime, 2,4,6-trimethylphenylcarbonyl-diphenyl oxide scale, hexafluorophosphoric trialkylphenyl rust salt, and the like. In the present invention, it is not limited to the above photopolymerization initiator, and other known photopolymerization initiators may be used. For example, the vicinal polyketalaldonyl compound described in the specification of U.S. Patent No. 2,367,660, the alpha-carbonyl compound described in the specification of U.S. Patent Nos. 2,367,661 and 2,367,670, and the specification of U.S. Patent No. 2,448,828. And acyloin ether, as described in the specification of U.S. Patent No. 2,722,512, which is described in the specification of U.S. Patent No. 2,722,512, the disclosure of which is incorporated herein by reference. A combination of a triallyl imidazole dimer/p-aminophenyl ketone described in the specification of the U.S. Patent No. 3,549,367, and a benzothiazole compound described in Japanese Patent Publication No. 51_4 8 5 1 6 /Trihalomethyl-s-tripper system-46-201122724 Compound, JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202- 232. An oxime ester compound or the like described in JP-A-2000-66385. Further, such photopolymerization initiators can also be used. The content of the photopolymerization initiator in the colored curable composition is preferably 〇·1% by mass to 1% by mass based on the total solid content of the composition, more preferably 0.5% by mass to 5.0% by mass. %. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can be favorably carried out to form a film having good strength. Arbitrary component In addition to the above components (A) to (D), the colored curable composition of the present invention may contain a known additive such as a binder polymer (alkali-soluble resin) or a solvent according to the purpose. Hereinafter, a known additive which can be added to the color hardening composition of the present invention will be described. Adhesive Polymer The colored hardenable composition of the present invention may contain an alkali-soluble resin as a binder polymer. The soluble resin may be a linear organic polymer, and has at least one base which promotes alkali solubility in a molecule (preferably a molecule mainly composed of an acrylic copolymer or a styrene copolymer). For example, an alkali-soluble resin such as a carboxyl group, a phosphoric acid group or a sulfonic acid group is appropriately selected from -47 to 201122724. Among them, it is further preferred to be soluble in an organic solvent and developable with a weak aqueous alkali solution. As the production of the alkali-soluble resin, for example, a known method by a radical polymerization method can be applied. The polymerization conditions for the temperature, the pressure, the type and amount of the radical initiator, the type of the solvent, and the like when the alkali-soluble resin is produced by the radical polymerization method can be easily set by the skilled artisan, and the experimental property can also be set. Conditional. As the linear organic polymer polymer, a polymer having a carboxylic acid in a side chain is preferred. For example, Japanese Patent Laid-Open No. 59-44615, Japanese Special Public Show No. 54-34327, Japanese Special Public Show No. 5 8- 1 25 77, Japanese Special Public Show No. 54-2 5957, and Japanese Special Open No. 59-53836 a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like described in each of Japanese Patent Publication No. 59-71 048, and In the case where the side chain has an acidic cellulose derivative of a carboxylic acid, a polymer obtained by adding a hydroxyl group to a hydroxyl group, or the like, a polymer having a (meth) acrylonitrile group in a side chain is more preferable. Good example. Among these, it is particularly suitable as a multicomponent copolymer of a benzyl (meth) acrylate / (meth) acrylate copolymer or a benzyl (meth) acrylate / (meth) acrylate / other monomer. Further, it is also possible to use a copolymer of 2-hydroxyethyl methacrylate. The polymer can be used in combination in any amount. In addition to the above, 2-hydroxypropyl (meth) acrylate/polystyrene monomer/predominant-48-201122724 methacrylate/, as described in JP-A-7-140654, Methacrylic acid copolymer, 2·hydroxy-3-phenoxypropyl acrylate/polymethylmethacrylate monomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl group Acrylate/polystyrene monomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene monomer/benzyl methacrylate/methyl Acrylic copolymer and the like. The specific constituent unit of the alkali-soluble resin is particularly preferably a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith. The term "(meth)acrylic acid" as used herein includes a generic term for acrylic acid and methacrylic acid. Hereinafter, (meth)acrylate is a generic term for acrylate and methacrylate. The other monomer which can be copolymerized with (meth)acrylic acid may, for example, be an alkyl (meth) acrylate, an aryl (meth) acrylate or a vinyl compound. Here, the hydrogen atom of the alkyl group and the aryl group may also be substituted by a substituent. Specific examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (methyl). Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Further, examples of the vinyl compound include styrene, a- Λ -49-201122724 methyl styrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, and N- Vinylpyrrolidone, tetrahydrofuranyl methacrylate, polystyrene monomer, polymethyl methacrylate monomer, CH2 = CR31R32, CH2 = C(R31)(COOR33) [here, R31 represents A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R32 represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R33 represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. 〕 Wait. These other copolymerizable other monomer types may be used alone or in combination of two or more. Preferred other copolymerizable copolymers are selected from the group consisting of CH2 = CR31R32, CH2 = C(R31) (COOR33), phenyl (meth) propionate, benzyl (meth) acrylate and styrene. At least one of them is particularly preferably ch2 = cr31r32 and / or CH2 = C(R31) (COOR33). The content of the alkali-soluble resin in the colored curable composition is preferably from 1% by mass to 15% by mass, more preferably from 2% by mass to 12% by mass, based on the total solid content of the composition. 3% by mass to 1% by mass. Solvent The color hardening composition of the present invention may contain a solvent as needed. As the solvent, there may be mentioned esters such as ethyl acetate, η-butyl acetate, isobutyl acetate 'amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate. , ethyl butyrate, butyl butyrate; alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, A Ethyl oxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; 3-oxypropionic acid-50-201122724 methyl ester, 3-oxypropionic acid ethyl group, etc. 3_oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-methoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropanoate, 2-oxy-2-methylpropane Ethyl acetate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, C Ethyl acetate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl carbitol acetate, butyl Carbitol acetate, etc.; ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl acid, methyl sarbuta acetate, ethyl赛路苏acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, Propylene glycol propyl ether acetate or the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-butane, 3-butanone, etc.; aromatic hydrocarbons such as toluene, xylene, and the like. Among these, it is more suitable as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib acetate, ethyl lactate, diethylene glycol dimethyl ether, Butyl acetate, methyl 3-methoxypropionate, 2-butanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl acid acetate, etc. The solvent may be used alone or in combination of two or more. Further, these solvents can also be used in the preparation of the above pigment dispersion liquid. -51-201122724 Other components The color-curable composition of the present invention may contain a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other chelating agents, a polymer compound other than the above-mentioned alkali-soluble resin, and adhesion promotion as necessary. Various additives such as agents, antioxidants, ultraviolet absorbers, anti-agglomerants, and the like. Thermal polymerization initiator The color-curable composition of the present invention contains a thermal polymerization initiator and is also effective. The thermal polymerization initiator may, for example, be a variety of azo compounds and peroxide compounds. Examples of the azo-based compound include an azobis compound, and examples of the peroxygen-based compound include a ketone peroxide, a peroxyketal, hydrogen peroxide, and a dialkyl peroxide. Dimercapto peroxide, peroxy ester, peroxydicarbonate, and the like. Thermal polymerization component In the color hardening composition of the present invention, it is effective to increase the film strength and to contain a thermally polymerizable component. As the thermal polymerization component, an epoxy compound is used. The epoxy group compound is a compound having two or more epoxy groups in the molecule, such as a bisphenol A type, a cresol novolak type, a biphenyl type or an alicyclic epoxy compound. Specifically, for example, regarding bisphenol A type epoxy compounds, in addition to EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD -7011R, ZX-1059, YDF-8170, YDF-170, etc. (above, Tohto Kasei Co., Ltd.), -52- 201122724 DENACOL EX-UOl, EX-1102 , EX-1103, etc. (above, Nagase ChemteX Corporation), Placcel GL-61, GL-62, G101, G102 (above, Daicel Chemical Industry (Daicel Chemical) Other than Industries, Ltd.), a bisphenol F-type epoxy compound or a bisphenol S-type epoxy compound similar to these may be mentioned. Further, an epoxy acrylate such as Ebecryl 3700, 3701, 600 (above, D a c c e 1 - C y t e c C 〇 m p a n y L t d ·) can also be used. Examples of the cresol novolac type epoxy compound include Aibotot YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN_704, etc. (above, Dongdu Chemical Co., Ltd.), Denarco EM-125 or the like (manufactured by Changchun Chemical Co., Ltd.), and examples of the biphenyl type epoxy compound include 3,5,3',5'-tetramethyl-4,4' diglycidyl group. Examples of the alicyclic epoxy compound include benzene, CELLOXIDE 2021, 2081, 2083, 2085, EPOLEAD GT-301, GT-3 02, GT-401, GT. -403, EHPE-3150 (above, Daisil Chemical Industry), SANTOHTO ST_3000 'ST-4000, ST-5 0 80, ST-5100, etc. (above Dongdu Chemical). Further, 1,1,2,2-indole (P-glycidyloxyphenyl)ethane, ginseng (P-glycidyloxyphenyl)methane, triglycidyl ginseng (base group) Ethyl)isomeric cyanurate, bismuth decyl phthalate, p-citric acid bis-53- 201122724 glycidyl ester, other amine type epoxy resin Avotot ΥΗ-434, YH- 4 3 4L, a bisphenol A type epoxy resin, a glycidyl ester modified by a dimer acid in a skeleton, or the like. Thermal polymerization inhibitor The thermal curing composition of the present invention may also be added with a thermal polymerization inhibitor. Regarding thermal polymerization inhibitors, such as hydroquinone, P-methoxyphenol, di-t-butyl-P-cresol, gallic phenol, t-butylcatechol, benzoquinone, 4,4'-sulfur double (3-Methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, and the like are useful. Preparation of Colored Curable Composition The colored hardening composition of the present invention can be prepared by the following steps: a coloring agent, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a specific copolymer (Comparative) It is preferable to add a mixing and dispersing step in which a mixture of arbitrary components is mixed with a solvent and mixed and dispersed using various mixers and/or dispersers. It is particularly preferable to prepare a pigment dispersion liquid in advance (A) when the colorant is a pigment, and to use the pigment dispersion liquid. Further, the mixing and dispersing step is preferably constituted by kneading dispersion and subsequent microdispersion treatment, but kneading dispersion may be omitted. An example of a method of preparing a color hardening composition of the present invention is shown below. A mixture of a pigment, a water-soluble organic solvent and a water-soluble inorganic salt is used as a light roll mill, a three-roll type roll mill, a ball mill, a drum mill, and a disperser. , kneading machine -54 - 201122724 (kneader), co-kneader (c〇_kneader), homogenizer, blender (blender), uniaxial or biaxial extruder, etc., while giving strong shear After the pigment is ground by force, the mixture is poured into water, and a stirrer or the like is used as a slurry. Then, the slurry is filtered and washed with water to remove the water-soluble organic solvent and the water-soluble inorganic salt, followed by drying to obtain a finely pigmented pigment. Further, the treatment for refining the pigment may be omitted. The beads are dispersed by a pigment, a dispersant and/or a pigment derivative and a solvent. Mainly use vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., with a particle size of 0.01 to 1 mm or oxidation The beads made of zirconium or the like are subjected to a fine dispersion treatment to obtain a pigment dispersion liquid. Further, a detailed description of the mixing and dispersion is described in "Paint Flowand Pigment Dispersion" by T.C. Patton (John Wiley and Sons Dry IJ, 1964). Then, after the (B) photopolymerizable compound, (C) photopolymerization initiator, (D) specific copolymer, and optional components are added to the obtained pigment dispersion as described above, the present invention can be obtained by a mixing and dispersing step. A colored hardening composition. Coloring pattern, color filter, and method of producing the same The coloring pattern of the present invention is characterized by being formed by the above-described color hardening composition of the present invention. The obtained colored pattern can suppress the planar deterioration caused by the coating, and can form a colored film having few defects. As a result, the colored pattern of the present invention can be applied to the pixel portion of the color filter, etc., from -55 to 201122724. The color filter of the present invention is characterized in that it has a colored pattern formed of the colored curable composition of the present invention on a substrate. Further, the method for producing a color filter of the present invention is characterized in that the coloring layer forming step of applying the colored curable composition of the present invention to a substrate by a spin coating method, a slit and a spin method, or a die coating method is provided. . Hereinafter, the color filter of the present invention will be described in detail (the method for producing a color filter of the present invention). In the method for producing a color filter of the present invention, first, the color hardening composition of the present invention is applied onto a substrate by a spin coating method, a slit method, a spin method, or a die coating method, directly or through another layer. step. By this step, a photocurable coating film is formed on the substrate, and then the coating film is exposed through a predetermined mask pattern. After the exposure, the uncured portion is removed by development with a developing solution, thereby forming a colored pattern. By performing this step in reverse, a pixel portion (colored pattern) of each color (three colors or four colors) can be formed on the substrate to obtain a color filter. According to the above method, a color filter for a liquid crystal display element or a solid-state imaging element can be produced with less difficulty in processing, high quality, and low cost. The steps of coating, exposure, and development will be described below. Coating step In the coating step, the colored curable composition of the present invention is applied onto a substrate by a spin coating method, a slit and a spin method, or a die coating method. -56- 201122724 In the case of the slit and spin method or the die coating method, the conditions vary depending on the size of the coated substrate, for example, by the die coating method applied to the glass substrate of the fifth generation (ll〇) When 〇mmxl250mm), the discharge amount of the colored curable composition from the slit nozzle is usually 500 to 2000 ml/sec, preferably 800 to 1800 ml/sec, and the coating speed is usually 50 to 300 mm. / sec, preferably 100 to 200 mm / sec. The solid content of the colored curable composition is usually from 1 〇 to 2 %, preferably from 13 to 18%. Further, when the glass substrate of the 3.5th generation is applied by the spin coating method at 720 mm x 600 mm, the discharge amount of the colored curable composition from the nozzle is usually 40 to 50 cc, and the number of application rotations is 500 to 1000 rpm. The solid content of the colored curable composition is usually from 1 to 25%, preferably from 18 to 22%. When the coating film of the color hardening composition of the present invention is formed on a substrate, the thickness of the coating film (after the prebaking treatment) is generally 0.3 to 5·0 μm, and desirably 0.5 to 4·0 μm, and most desirable. It is 0.8~3.0μηι. Next, the substrate to which the color hardening composition of the present invention is applied will be described. As the substrate in the present invention, for example, an alkali-free glass, a soda glass, a Pyrex (PYREX: registered trademark) glass, a quartz glass, and a transparent conductive film for liquid crystal display elements can be used. For these, or a photoelectric conversion element substrate such as a solid-state imaging element, for example, a germanium substrate or the like, and a plastic substrate. On these substrates, a black matrix for isolating each pixel is usually formed, and a transparent resin layer for promoting adhesion or the like may be provided. The plastic substrate preferably has a gas barrier layer (gas barrier - 57 - 201122724 layer) and/or a solvent resistant layer on its surface. In addition, the present invention can also be applied to a substrate for driving a thin film transistor (TFT) in a thin film transistor (TFT) color liquid crystal display device (hereinafter referred to as a "TFT substrate for liquid crystal driving"). The color hardening composition forms a colored pattern to produce a color filter. The substrate in the TFT liquid crystal driving substrate may, for example, be glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidamine or polyimine. These substrates may be subjected to a suitable pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, ion plating, sputtering, a gas phase reaction method, or a vacuum vapor deposition, as needed. For example, a substrate having a passivation film such as a nitride film or the like formed on the surface of the TFT liquid crystal driving substrate or the surface of the driving substrate may be used. Further, when a colored pattern is formed on the TFT-type liquid crystal driving substrate by using the color-curable composition of the present invention, a photomask used at the time of exposure is preferably a pattern other than a pattern for forming a pixel. It is a pattern in which a through hole or a 3-shaped depression is also provided. As described above, after the photocurable coating film is formed, a prebaking treatment is usually performed. Further, vacuum treatment may be performed before prebaking as necessary. The vacuum drying condition is usually a vacuum of 0.1 to 1. Otorr, preferably about 0.2 to 0.5 torr. For pre-bake processing, a hot plate or an oven may be used, and in a temperature range of 50 to 140 ° C (preferably 70 to 11 ° C), -58- 201122724 10 to 3 The condition of 00 seconds is carried out. Here, the prebaking treatment may be performed by high frequency processing or the like. Also, high frequency processing can be used alone. Exposure step The exposure step is such that after the photocurable coating film is formed on the substrate, the coating film is exposed through a predetermined mask pattern. At this time, the radiation to be used is particularly preferably an ultraviolet ray such as a g line, an h line, an i line, or a j line. Further, in the case of manufacturing a color filter for a liquid crystal display device, it is preferable to use a proximity type exposure machine or a mirror projection machine to perform exposure mainly using h-line and i-line. Developing Step The developing step 'is an uncured portion after the developing solution is eluted and exposed, and only the hardened portion remains. The development temperature is usually 20 to 30 ° C, and the development time is 20 to 90 seconds. In addition, the developer can be used as long as it can dissolve the coating film of the photocurable coloring curable composition in the uncured portion and does not dissolve the hardened portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. The above-mentioned solvent which can be used when preparing the pigment dispersion liquid of the present invention or the colored curable composition can be mentioned. The alkaline aqueous solution may, for example, be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine or dimethylethanolamine. Tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo 45,4,0:1-7- -59- 201122724 The alkaline compound is dissolved in an aqueous solution having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline aqueous solution in an appropriate amount. The development method may be any one of a dipping method, a shower method, and a spray method, or a combination of a swing method, a spin method, an ultrasonic method, and the like. Before the developer is contacted, the developed surface is wetted with water or the like in advance, and uneven development can be prevented. Further, the substrate can be tilted and developed. After the development treatment, the cleaning step of removing the remaining developer after washing is performed, and after drying, in order to completely harden, heat treatment (post-baking) is performed. The washing step is usually carried out in pure water. In order to save the liquid, pure water can be used for cleaning at the end, and the used pure water is used at the beginning of washing, the substrate is tilted and washed, and ultrasonic irradiation is applied. After the washing step, after removing water and drying, it is usually subjected to heat treatment at about 20 ° C to 250 ° C. This heat treatment (post-baking) can use a heating means such as a heating plate, a convection oven (hot air circulation dryer), or a 髙 frequency heating machine to form the coating film after development. Continuous or batchwise. According to the desired number of hue, each of the colors is sequentially and repeatedly performed in order, whereby a color filter in which a plurality of color patterns (pixels) of plural colors are formed can be produced. The use of the color hardening composition of the present invention is mainly described for the use of the color filter of -60-201122724', but can also be applied to form a black matrix which separates each colored pixel constituting the color filter. . The black matrix can be formed by exposing, developing, and further post-baking the pigment dispersion of the present invention using a black pigment such as carbonium, titanium black or the like as a pigment to promote hardening of the film. Liquid crystal display element The liquid crystal display element of the present invention is a liquid crystal display element using the color filter of the present invention. More specifically, 'the alignment film formed on the inner surface side of the color filter of the present invention is obtained by facing the electrode substrate and sealing the liquid crystal after the gap portion is filled" to obtain the liquid crystal display element of the present invention. Panel. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the examples below. Further, unless otherwise specified, "%" and "parts_ are all based on mass. The synthesis of halogenated scented cyanine pigments produces phthalocyanine from phd.halodinitrile and zinc chloride as raw materials. The halogenation is carried out by mixing sulfonium chloride 3.1 parts of 'anhydrous aluminum chloride 3 · 7 parts, 4 parts of sodium chloride 4 · 4 parts of zinc phthalocyanine, and dropping 2.2 parts of bromine at 40 ° C. The above mixture was reacted at 80 ° C for 15 hours, and then the reaction mixture was put into water to precipitate a portion of the crude zinc bromide phthalocyanine pigment. The aqueous slurry was filtered and washed with hot water at 80 ° C to make it 9 0. (: Dry, and get 61 - 201122724 2.6 parts of refined part of zinc bromide phthalocyanine pigment. 1 part of this part of zinc bromide phthalocyanine pigment, crushed sodium chloride 7 parts, 2 The diol I.6 parts and the xylene 0.09 parts were fed to an open-type kneader at 10 Torr. The mash was kneaded for 6 hours. After the kneading was taken out, 80. (: 1 水 of water, After stirring for 1 hour, filtration, hot water washing, and drying were carried out to obtain a pulverized partial zinc bromide phthalocyanine pigment. The zinc phthalocyanine pigment is analyzed by the halogen content according to the mass analysis, and the average composition is ZnPCBriQCl4H2 (Pc; phthalocyanine), and an average of 10 bromines in one molecule. Further, by transmission electron microscopy (Japan Electronics Co., Ltd. (JE0L) The average 値 of the primary particle diameter measured by JEM-2010) is 0.065 μηι. Synthesis Example 1 Synthesis of polyester resin (i-Ι) η octane acid 6.4 g, ε·caprolactone 200 g 5 g of tetrabutyl titanium oxide (IV) was heated at room temperature for 8 hours, and then cooled to room temperature to obtain a polyester resin (i-1). The flow chart is as follows.

^7^15*11 〇+ Η〇1〇7Η15-π Synthesis Example 2 Synthesis of Resin (J-1) Mixed Polyethylenimine (SP-018, number average molecular weight 1,800, Japanese catalyst ( Nippon Shokubai Co., Ltd.) 10 g and the aforementioned polyester resin 62-201122724 (il) 100 g, and heated at 120 ° C for 3 hours to obtain an intermediate (J_1B). Then, let cool to 65. (:, 200 g of propylene glycol 1-monomethyl ether 2-acetate (hereinafter referred to as PGMEA) containing 3.8 g of succinic anhydride was slowly added and stirred for 2 hours. Then, PGMEA was added to obtain a resin (J-1). PGMEA 10% by mass solution. Resin (1-1) has a side chain derived from a polyester resin (i-Ι) and a carboxyl group derived from succinic anhydride. The synthesis scheme is as follows: 〇Ο HO- 40 -C7Hirn + Polyethylenimine +ch2ch +ch2ch2-ijj+i2

〇7Ηί5·Π ~H -4cH2CH2-NH2l-ml -fcH2CH2-NH2}rr,2 f CH2CH2-NH-]-ntl&lt; vy+k &quot;N xo2h 〇t3-° Intermediate (J-1B) fcH2GH2-N -[; feH^HrN^ . |cH2CHrN-}(2 -f〇H2CH2--NH2fm1 -j-CH2GH2-NH2}m2 +CH2CH2_NH Soil^O-^^xs^Ol^-CyH^ne〇-|5s^Sx^〇]-H Resin ( Jl) Preparation of a dispersion of green pigmented zinc halide phthalocyanine A high-speed disperser "TSC-6H" manufactured by Aimex Co., Ltd., which has been filled with cerium oxide beads having a diameter of 55 mm. In the above, 14.9 parts of the brominated ruthenium cyanine pigment (referred to as PG58) obtained in the above-mentioned, -63-201122724 BYK Chemie company's acrylic dispersant "Β Υ Κ - 2 0 0 1" 7.1 parts , PGME A 78 parts, at 2000 rpm, stirring for 8 hours, prepared a partial brominated zinc halide phthalocyanine pigment dispersion (green pigment PG58 dispersion). Yellow pigment PY1 50 dispersion will be prepared as Pigment CI Pigment Yellow 150 (PY150) 15 parts (average particle size 60 nm), 7.5 parts of the above resin (Jl), 77.5 parts of PGMEA, in a bead mill "TSC-6H" (using a chromium oxide diameter of 0.3 mm) The beads were mixed and dispersed for 3 hours to prepare a dispersion of the yellow pigment PY 150. The components of the following composition were added and stirred and mixed to obtain the color hard of Example 1. Composition coating liquid (color resist liquid). • Dispersion of green pigment PG58... 3 2.50 parts • Dispersion of yellow pigment PY150... 11.20 parts • Dipentaerythritol hexaacrylate a mixture with a mixture of dipentaerythritol pentaacrylate and a succinic acid derivative of dipentaerythritol pentaacrylate (trade name: TO-1 3 82 (M-5 20) East Asia Synthetic System) ... 3.94 parts • Photopolymerization initiator: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9Η·oxazol-3-yl]-, 1-(〇乙醯基肟) (trade name: IRGACURE ΟΧΕ02 Ciba) ...1 .0 86 parts • Allyl methacrylate/methacrylic acid (=8 0/2 0 [mole ratio]) copolymer (weight average molecular weight: 30,000). ..1.1 86 parts • Propylene glycol monomethyl ether acetate...25.36 parts • Antioxidant (trade name: LA-52 ADEKA Corporation)... -64 - 201122724 0 0 8 0 copies *Special fluorine &lt; Surfactant (previously exemplified compound: W-1) ... 0.017 parts • 3-ethoxyethyl propionate... 24.60 parts of Example 2-25 except the specific fluorine-based surfactant of Example 1. (previously Illustrative compound: W-1) 0.017 parts were changed to the specific fluorine-based surfactants (all of the above-exemplified compounds) shown in Table 1 and Table 2, and the same procedure as in Example 1 was carried out, and Example 2 was prepared. Example 2 A colored hardening composition (color resist liquid). Comparative Example 1 In Example 1, except that a specific fluorine-based surfactant (the above-exemplified compound: W-1) was changed to a comparative fluorine-based surfactant described below: Comparative Compound W-a, and Examples 1 was carried out in the same manner, and the colored curable composition (color resist liquid) of Comparative Example 1 was prepared. W-a

(CF2)6F 20 mass ° / 〇

-W ch3 •CH2CH2— 0

-H 10 80% by mass

Mw: 1 500 Comparative Example 2 In Example i, 'the specific fluorine-based interface' active agent (the above-exemplified -65-201122724 compound: wl) was changed to the comparative fluorine-based surfactant shown below: The color hardening composition (color resist liquid) of Comparative Example 2 was prepared in the same manner as in Example 1 except for the compound Wb. W—b ch3 c—(CH2)4CH3 &lt;〇/\^(CF2)6F cf'O— -ch2ch——0- -Η 20% by mass 80% by mass

CH

I CH2-c-

Mw: 1 500 Comparative Example 3 In Example 1, except that a specific fluorine-based surfactant (the above-exemplified compound: W-1) was changed to a comparative fluorine-based surfactant described below: a comparative compound Wc, In the same manner as in Example 1, the colored curable composition (color resist liquid) of Comparative Example 3 was prepared. W-c

2 Η C C-C- 5 mass 0/〇

95% by mass

Mw: 1500 Comparative Example 4 In Example 1, except that a specific fluorine-based surfactant (the above-exemplified compound: W-1) 0. 〇1 7 parts was changed to the comparative fluorine-based interface activity-66- In the same manner as in Example 1, except that the compound wd was 0.020 parts, the color-curable composition (color resist liquid) of Comparative Example 4 was prepared. Wd CH3 ch3 -fcH2-Cj- Γ人" CH2CH3 -ch2ch —0- 32 CH: 10 0% by mass 90% by mass

Mw: 1 500 Comparative Example 5 In Example 1, except that 0.017 parts of a specific fluorine-based surfactant (the above-mentioned exemplified compound: W-1) was changed to a comparative fluorine-based surfactant shown below: Comparative Compound We 0.020 In the same manner as in Example 1, the color-curable composition (color resist liquid) of Comparative Example 5 was prepared. W_θ -fcH2* ch3 〇人0 20% by mass to 4ch2 CH, -C- + cyo ch2ch3 CH2CH Ο η—Η 14 80% by mass

Mw: 800 Comparative Example 6 In Example 1, except that a specific fluorine-based surfactant (the above-mentioned exemplified compound: W-1) was changed to a comparative fluorine-based surfactant described below: a comparative compound wf, Example 1 was carried out in the same manner to prepare a color-curable composition (color resist liquid) of Comparative Example-67-201122724.

-CH ch3 20% by mass CH3 seven h24-

Gh2ch3 1 CH2CH—ο 80% by mass -Η ίο

Mw: 20000 Comparative Example 7 In Example 1, except that a specific fluorine-based surfactant (the above-exemplified compound: W-1) was changed to a comparative fluorine-based surfactant described below: Comparative Compound W-g, The colored curable composition (color resist liquid) of Comparative Example 7 was prepared in the same manner as in Example 1. W—g ch3 --ch2—c· ch3 —(-CH2-C-j- ^\^x(CF2)18F 20% by mass Mw :.30000

0 CH2CH ch2ch—80% by mass 3 〇

-H Comparative Example 8 In the first embodiment, the specific fluorine-based surfactant (the above-mentioned exemplary compound: W-1) was changed to the comparative fluorine-based surfactant described below: the comparative compound Wh, and was carried out. In the same manner as in Example 1, the colored curable composition (color resist liquid) of Comparative Example 8 was prepared. -68- 201122724

0^0 /\^(°ρ2)δρ

80% by mass Mw: 11 000 20% by mass. Comparative Example 9 In Comparative Example 3, the same procedure as in Comparative Example 3 was carried out except that the amount of the comparative fluorine-based surfactant (the comparative compound Wc) was changed to 0.02 5 parts. The color hardening composition (color resist liquid) of Comparative Example 9 was prepared. Comparative Example 1 0 In Comparative Example 3, the color hardening composition of Comparative Example 9 was prepared in the same manner as in Comparative Example 3 except that the amount of the comparative fluorine-based surfactant (the comparative compound Wc) was changed to 0.220. (color photoresist). Production and Evaluation of Evaluation Samples 1. Evaluation of Coating Pattern and Drying Unevenness 1-1. 550 mm x 650 mm Glass Substrate Each of the colored curable compositions (color resist liquid) prepared in each of Examples and Comparative Examples was at 550 mm x 650 mm. The glass substrate (1737, manufactured by Corning Co., Ltd.) was applied to a wet film thickness of 25 μm by a slit die at a coating speed of 100 mm/s, a coating interval of -69 to 201122724, and a coating flow rate of 1.3 ml/s. The color drying film was formed on the substrate by vacuum drying in a vacuum drying chamber at a reaching pressure OJTorr. The substrate having the dried colored film was observed with a Na lamp and a white lamp, and the coating streaks and unevenness of the colored film were evaluated according to the following criteria. The results are shown in Yiyi 1 and Table 2. The results of this evaluation are described in the table of "coating streaks" and "dry unevenness". L-2.2, 880 mm x 3, 080 mm glass substrate: large substrate The color hardening composition (color photoresist liquid) prepared in each of the examples and the comparative examples was placed on a glass substrate (large substrate) of 2,880 mm x 3,080 mm. Applying a slit die at a coating speed of 15 mm/s, a coating gap of mlμηη, and a coating flow rate of 1.8 ml/s to a wet film thickness of 25 μm, drying and forming a colored film on the substrate, similarly The following coatings were used to evaluate the coating streaks and uneven drying of the colored film. The results are shown in Table 1 and Table 2. The evaluation results are shown in the table of "large substrate coating streaks" and "large substrate drying unevenness". Coated markings 〇: No coating markings. △: There is only a coating streak at the end portion of the circumference. X: There are coating marks on the end and the center of the circumference. Uneven drying (interference fringes) 〇: No uneven drying (interference fringes) was observed. Δ: Only some were observed, but the allowable range. X: Drying unevenness (interference fringe) exceeding the allowable range was observed. -70-201122724 2. Evaluation of image defects (coating shrinkage) was carried out so that the wet film thickness was 25 μm, and it was carried out in a vacuum drying chamber. The substrate was dried in an oven at 90 ° C for 90 seconds (pre-baked) before vacuum drying. Then, exposure was carried out at 50 mJ/cm 2 (illuminance: 20 mW/cm 2 ) over the entire coated position, and the film-based alkali developer CDK-1 (Fuji Film Electronic Materials Co.) was used after exposure. , 1% aqueous solution of Ltd.) was covered and allowed to stand for 60 seconds. After standing, the pure water was sprayed in a spray form to wash away the developer. Further, the coating film subjected to the exposure and development treatment as described above is subjected to heat treatment (post-baking) in an oven at 220 ° C for 1 hour, and a colored resin film for forming a color filter is formed on the glass substrate, thereby producing a coating film. Colored filter substrate (color filter). On the obtained color filter, the same coloring curable composition as in Example 3 was applied by a slit die at a coating speed of 100 mm/s, a coating gap of mlμηη, and a coating flow rate of 1.3 ml/s to make it wet. The film thickness was changed to 25 μm, and the surface after coating was observed with a sodium lamp and an optical microscope, and image defects (coating shrinkage) were evaluated according to the following criteria. The results are shown in Tables 1 and 2. Image defects 〇: No image defects. △: Although there was no image defect, a slight unevenness was confirmed in the surface. X: A slight image defect was observed. 3. Evaluation of liquid crystal contamination (liquid crystal specific resistance) The color hardening composition adjusted in each of the examples and the comparative examples was coated with a glass substrate of 100 mm×100 mm (EAGLE 2000, manufactured by Corning Co., Ltd.). The coating was applied to a dry film thickness of 2 μm (wet film thickness Π μηη), and vacuum drying was performed in a vacuum drying chamber so as to reach a vacuum degree of 0.5 Torr. The dried substrate was dried with a hot plate at 80 ° C x 12 ° se C, and then subjected to full exposure at 40 mJ/cin 2 and then baked at 230 ° C for 40 minutes in a convection oven. After peeling off the completed coating film from the substrate, 9 mg was mixed into 2 g of liquid crystal (MLC-6608, manufactured by Merck), and after heating at 120 ° C for 5 hours, using an ultra-small galvanometer (ADC) (ADC Corporation) Digital High Resistor/Micro Current Meter 8 3 40 A) Determine the specific resistance of the liquid crystal. The evaluation results were determined as follows. 〇: specific resistance is l.〇xl〇12[Q.cm] or more △: specific resistance is 1.0x10&quot;above and less than l.〇xl〇12[Q'cm] x : specific resistance is less than 1.0 x 1 〇11 [ Ω · cm ] Generally, the liquid crystal display has a higher number of resistance than the resistor, and the degree of contamination of the liquid crystal is low, and the reliability of the panel is excellent. Further, the specific resistance of the liquid crystal itself is usually about 1. 〇 xl 〇 13 [Q * cm] - 72 - 201122724 [Table 1] Surfactant (specific copolymer) Evaluation result Type of use (parts) Coating stain drying Large-scale substrate coating speckle large substrate drying uneven image defect liquid crystal specific resistance Example 1 W-1 0.017 〇〇〇〇〇〇 Example 2 W-2 0.010 〇〇〇〇〇〇 Example 3 W-3 0.017 〇 〇〇〇〇〇 Example 4 W-3 0.010 〇〇〇〇Δ 〇 Example 5 W-3 0.020 〇〇〇〇Δ 〇 Example 6 W-4 0.017 〇〇〇〇〇〇 Example 7 W-5 0.020 〇〇〇〇〇〇Example 8 W-6 0.020 〇〇〇〇Δ 〇Example 9 W-7 0.017 〇〇〇〇Δ 〇Example 10 W-8 0.017 〇〇〇〇〇〇Example 11 W -9 0.017 〇〇〇〇〇〇 Example 12 W-10 0.017 〇Δ 〇Δ 〇〇 Example 13 W-11 0.017 Δ 〇 Δ 〇 Δ 〇 Example 14 W-3 0.045 Δ 〇 Δ 〇 Δ Δ Example 15 W-16 0.017 〇〇〇〇〇〇Example 16 W-17 0.017 〇〇〇 Square. Square -73-201122724 [Table 2]

Surfactant (Specific Copolymer or Comparative Surfactant) Evaluation Results: Thin Application, Drying, Large Substrate, Large Substrate Image, Liquid Crystal Ratio (Parts), Patterning, Uneven Coating, Patterning, Drying, Uneven Resistance, Example Π W-18 0.045 〇 〇〇〇〇〇 Example 18 W-19 0.010 〇〇〇〇〇〇 Example 19 W-20 0.017 〇〇〇〇〇〇 Example 20 W-21 0.010 Δ 〇Δ 〇Δ 〇 Example 21 W-22 0.020 Δ 〇Δ 〇Δ 〇 Example 22 W-23 0.017 〇〇〇〇〇〇 Example 23 W-3 0.18 Δ 〇 Δ 〇 Δ Δ Example 24 W-18 0.99 Δ Δ Δ Δ Δ Δ Example 25 W -24 0.017 〇〇〇〇〇〇Comparative Example 1 Wa 0.017 Δ X Δ X 〇X Comparative Example 2 Wb 0.017 XXXX 〇X Comparative Example 3 Wc 0.017 XXXX 〇X Comparative Example 4 Wd 0.020 〇〇〇〇XX Comparative Example 5 We 0.020 Δ X Δ X 〇X Comparative Example 6 Wf 0.017 Δ 〇 Δ 〇 XX Comparative Example 7 wg 0.017 X 〇 X 〇 XX Comparative Example 8 Wh 0.017 Δ X Δ X Δ X Comparative Example 9 Wc 0.025 XXXXXX Comparative Example 10 Wc 0.220 XXXXXX-74-201122724 As shown in Table 1 and Table 2, it is known that polystyrene containing (D) a repeating unit AQ represented by the formula (1) and a repeating unit B and determined by gel permeation chromatography is used. In Examples 1 to 25 of the colored curable composition of the present invention in which the converted weight average molecular weight is 100 00 or more and 10000 or less, it is possible to suppress the occurrence of coating streaks, uneven drying, and image defects. The liquid crystal specific resistance is good. In addition, when the large-sized substrate is used and the coating speed and the coating flow rate are increased, the coloring-curable composition of the present invention can effectively suppress the occurrence of coating streaks and uneven drying, as in the case of using a small-sized substrate. This is especially useful when making color filters on an area substrate. Example 2 Synthesis of Dye A1 15 parts of SULFO RHODAMINEB (manufactured by Kanto Kagaku), 150 parts of chloroform and 9.8 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device. After maintaining at 20 ° C or lower with stirring, 12.0 parts of sulfite chloride was added dropwise. After the completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was maintained at the same temperature for 5 hours, followed by cooling to 20 ° C. The reaction solution after cooling was maintained at 20 ° C or lower while stirring, and a mixed liquid of 13.9 parts of 2 ethylhexylamine and 24.5 parts of triethylamine was added dropwise thereto. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. Next, the resulting reaction mixture was evaporated to dryness with a rotary evaporator, and then a small amount of methanol was added and stirred vigorously. The mixture was added to a mixed liquid of 371 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were filtered, washed carefully with ion-exchanged water, and dried under reduced pressure at 60 ° C to give 14.7 parts of dye A1. The dye A1 is a mixture of the component (a) shown below and the component (b) -75- 201122724.

Adjustment of A1 Resin Solution B 1 In a flask equipped with a stirrer 'thermometer, a reflow cooling tube, a dropping funnel, and a nitrogen introduction tube, 182 g of propylene glycol monomethyl ether acetate was introduced, and the gas atmosphere in the flask was taken from Air is replaced by nitrogen. Thereafter, after raising the temperature to 10 ° C, a monomethacrylate of 70.5 g (0-40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and a tricyclodecane skeleton was dropped ( Addition of 2,2'" azobisisobutyronitrile to a mixture of 22.0 g (0.10 mol) and propylene glycol monomethyl ether acetate 136 g manufactured by Hitachi Chemical Co., Ltd. (FA-513M) A solution of 3.6 g was added and stirring was continued at 10 °C. Next, the gas atmosphere in the flask was changed from nitrogen to air, and glycidyl methacrylate was 35.5 g [0.25 mol, (50 mol% relative to the carboxyl group of methacrylic acid used in the reaction)], Further, dimethylglycolylmethylphenol oxime. 9 g and hydroquinone. 145 g were charged into the flask and the reaction was continued at 110 ° C to obtain a resin solution Bi having a solid content acid value of 79 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 30, and 〇〇(^) was added in the order shown in the following order, and stirred and mixed to prepare an example containing a dye as a colorant. 26 color hardening composition -76- 201122724 coating liquid (color photoresist). CI pigment blue 15:6 dispersion adjustment colorant: CI pigment blue 15:6 acrylic pigment dispersant: BYK-163 (BYK Chemie propylene glycol monomethyl ether acetate was mixed with the above components, and dispersed by a bead mill "TSC-6H", and the pigment dispersion liquid was first adjusted. Adjustment of coloring curable composition Next, the following components were added to the pigment dispersion liquid. Coloring photosensitive roll colored photosensitive resin composition of Example 26 mixed with a dye as a coloring agent Formulation coloring agent: Dye A 1 Resin: Resin solution B1 Photopolymerizable compound: dipentaerythritol hexaacrylate (曰本Chemical preparation, photopolymerization initiator: 〇XE-01 (manufactured by Ci.ba. Specialty. Chemicals Co., Ltd.) Fluorine-based surfactant (previously exemplified compound: Wl) Solvent: 4-hydroxy-4-methyl Ketopentanone The colored photosensitive resin group Example 1 of Example 26 was evaluated in the same manner. The results are shown in Table 3 below. 2.96 parts by volume, 0.74 parts, 20.23 parts, and the pigments were sufficiently mixed to obtain a f-fat composition. 2 parts 2 3.2 1 part 7:3 9 parts 2.22 parts 〇· 0 1 7 parts 42·72 parts and implementation-77- 201122724 [Table 3] Surfactant (specific copolymer) Evaluation result mm Usage (parts Coating uneven drying coating large substrate coating speckle large substrate drying unevenness image defect liquid crystal specific resistance Example 26 W-1 0.017 〇〇〇〇〇〇 From the results of the above Table 3, even in the case of containing dye as a coloring agent When the colored photosensitive resin composition of the present invention is used for a large substrate, the coating streaks, uneven drying, and image defects can be suppressed, and the specific resistance of the liquid crystal is good. [Simplified description of the drawing] Sister. /1 \\ [Main component symbol description] None. -78-

Claims (1)

201122724 VII. Patent application scope: 1. A coloring hardening composition containing (A) a coloring agent, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a repeating unit represented by the formula (1) and a repeating unit B, and a polystyrene-equivalent copolymer having a weight average molecular weight of 1,000 or more and 10,000 or less as measured by gel permeation chromatography, R1 -|ch2-c^- R2 I ch2-c- P -R°-(CF2)nF repeating unit oq (1) -〇--R3 repeating unit B In the formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group; RG represents an alkylene group having a carbon number of 1 or more and 4 or less; L represents an alkylene group having a total carbon number of 3 or more and 6 or less; and R3 represents a hydrogen atom or an alkyl group having a carbon number of 1 or more and 4 or less; p is Represents the mass percentage of the polymerization ratio of the repeating unit, and P represents a number of 11% by mass or more and 80% by mass or less; q is a mass percentage representing a polymerization ratio of the repeating unit B, and q represents 20% by mass or more and 90% by mass % below 値; r represents an integer of 1 or more and 18 or less; η represents an integer of 1 or more and 1〇 or less. 2. The colored hardening composition as claimed in claim 1 wherein the repeating unit in the general formula (1) is the following repeating unit: -79- 201122724 R1 P^\^(CF2)nF Repeating unit A In the repeating unit A, R1 represents a hydrogen atom or a methyl group; p is a mass percentage representing a polymerization ratio of the repeating unit A, and represents 10% by mass or more and 80% by mass or less The number 値; η represents an integer of 1 or more and 10 or less. 3. The colored hardening composition of claim 1, wherein the L in the repeating unit is an alkyl group represented by the following formula (2) or (3): R 4 ch2ch (2) R4 Ichch2 (3) In the formula (2) and the formula (3), R4 represents an alkyl group having 1 or more and 4 or less carbon atoms. -80-201122724 4. The colored hardening composition of claim 3, wherein the R4 is an ethyl group. 5. The color-hardening composition of claim 1, wherein the weight average molecular weight of the (D) copolymer is 15 (30 or more and 5000 or less. 6. If the patent application is the first item) The curable composition 'where p represents a number 20 of 20% by mass or more and 60% by mass or less, and q represents a number 〇 of 4% by mass or more and 80% by mass or less. 7. Color hardening as in the first application of the patent scope The composition 'in which r is an integer of 6 or more and 18 or less. 8 · The colored hardening composition of the first aspect of the patent application' wherein the copolymer contains 1 in terms of the total mass of the copolymer 0% by mass or more and 80% by mass or less of the repeating unit A% and containing 20% by mass or more and 90% by mass or less of the repeating unit B with respect to the total mass of the copolymer. 9 · Patent Application No. 1 The colored hardening composition, wherein the content of the copolymer in the colored curable composition is 0.005 mass 5% by mass. 10. A coloring pattern which is colored by the first item of the patent application scope Formed by a hardening composition. A color filter having a colored pattern as in claim 10 of the patent application. 12. A method of manufacturing a color filter having a spin coating method on a substrate, a slit and a rotation method Or a dip coating method of applying the coloring layer forming step of the color hardening composition according to any one of the above items 1 to 9; and exposing the formed coloring layer into a pattern, and A coloring pattern forming step of developing a color pattern to form a color pattern. A liquid crystal display element using a color filter as in claim 1 of the patent application. -82- 201122724 IV. Designated representative figure. (1) The case The designated representative figure is: None. (2) The symbolic symbol of the representative figure is simple: 〇5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: