JP2008242273A - Colored curable resin composition, colored pattern forming method, colored pattern, method for manufacturing color filter, color filter and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable resin composition which causes no coating defect and less variation in film thickness even in high-speed coating, ensures good film surface conditions of an obtained color filter, and can provide such good color properties as high color purity and high contrast, a colored pattern forming method, a colored pattern, a color filter obtained using the colored curable resin composition, a method for manufacturing the same, and a liquid crystal display device including the color filter. <P>SOLUTION: The colored curable resin composition includes (a) a color material, (b) a solvent, (c) at least one species selected from the group consisting of polymerizable monomers and binder resins, (d) a photopolymerization initiator and (e) a polymer surfactant having a fluoroaliphatic group in a side chain. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored curable resin composition, a colored pattern forming method, a colored pattern, a method for producing a color filter, a color filter, and a liquid crystal display element.

  A color filter contains a binder resin and / or monomer, a photopolymerization initiator, and other components in a solvent dispersion composition of a colorant such as an organic pigment or an inorganic pigment, and forms a colored photosensitive composition. It is manufactured by the photolithographic method.

  In recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). With this trend of expanding applications, advanced color characteristics such as chromaticity and contrast. Has come to be required. In addition, in the image sensor (solid-state imaging device) application, a device having high color characteristics is also demanded.

  In addition, with the increase in size of the substrate, the method of applying the colored photosensitive composition has been shifted from the spin coating method to the slit coating method (also referred to as die coating or casting coating) for the purpose of improving productivity. Among them, a composition suitable for the coating method is required, and as such a composition, a composition having specific physical properties controlled is disclosed (for example, see Patent Document 1). In recent years, with the widespread use of large-sized liquid crystal displays and the like, further increase in the size of substrates has progressed, and there has been a demand for unprecedented high-speed coating in the slit coating method. However, these techniques have a problem that there are still many coating defects when the slit coating speed is set to 200 mm / sec on a glass substrate for producing a color filter.

  On the other hand, a technique for improving the development resistance of a non-photosensitive coating solution using a specific surfactant has been disclosed (see, for example, Patent Document 2). It has not been reported for curable resin compositions.

WO2005 / 075524A1 JP 2004-221944 A

The present invention has been made in consideration of the above-mentioned problems. Even when the slit coating speed is set to a high speed of 200 mm / sec or more on a glass substrate for producing a color filter, there is no coating defect, and the film A colored curable resin composition, a colored pattern forming method, and a colored pattern, which have good thickness and low color unevenness, good color filter film surface shape, high color purity and high contrast, The purpose is to provide.
Another object of the present invention is to provide a color filter having a high contrast, a method for producing the same, and a liquid crystal display device including the color filter, using the colored curable resin composition of the present invention. It is in.

  In order to achieve the above object, the configuration of the present invention is as follows.

<1> (a) a coloring material, (b) a solvent, (c) at least one selected from the group consisting of a polymerizable monomer and a binder resin, (d) a photopolymerization initiator, and (e) a fluoroaliphatic group. A colored curable resin composition comprising a polymeric surfactant in a side chain.
<2> The fluoroaliphatic group in the polymer surfactant (e) having a fluoroaliphatic group in the side chain is derived from a fluoroaliphatic compound produced by a telomerization method or an oligomerization method. The colored curable resin composition according to <1>, wherein the colored curable resin composition is.

<3> The <1>, wherein the fluoroaliphatic group in the polymer surfactant (e) having a fluoroaliphatic group in the side chain is a group represented by the following general formula (I): Or the colored curable resin composition as described in said <2>.

In the formula, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents a single bond or a divalent linking group, m represents an integer of 0 or more, n Represents an integer of 1 or more.

<4> A colored pattern forming method comprising a step of applying the colored curable resin composition according to any one of <1> to <3> by a slit coating method.
<5> A colored pattern formed by the colored pattern forming method according to <4>.

<6> A method for producing a color filter comprising a step of forming a colored pattern by applying the colored curable resin composition according to any one of <1> to <3> by a slit coating method. .
<7> A color filter manufactured by the manufacturing method according to <6>.
<8> The color filter according to <7>, wherein the contrast is 5000 or more.
<9> A liquid crystal display device using the color filter according to <8>.

According to the present invention, even when the slit coating speed is set to a high speed of 200 mm / sec or more on a glass substrate for the production of a color filter, there is no coating defect, the film thickness is small, and the obtained color filter It is possible to provide a colored curable resin composition, a colored pattern forming method, and a colored pattern that have good film surface properties, high color purity, and good color characteristics such as high contrast.
Further, according to the present invention, by using the colored curable resin composition of the present invention, a color filter having a high contrast, a method for producing the same, and a liquid crystal display device including the color filter can be provided. .

Hereinafter, the present invention will be described in detail.
[Colored curable resin composition]
The colored curable resin composition of the present invention comprises (a) a color material, (b) a solvent, (c) at least one selected from the group consisting of a polymerizable monomer and a binder resin, (d) a photopolymerization initiator, and (E) It contains a polymeric surfactant having a fluoroaliphatic group in the side chain.
Hereinafter, the components in the present invention will be described in detail.

<(E) Polymer surfactant having fluoroaliphatic group in side chain>

  The curable resin composition of the present invention contains (e) a polymer surfactant having a fluoroaliphatic group in the side chain. The fluoroaliphatic group of the polymeric surfactant having a fluoroaliphatic group in the side chain in the present invention (hereinafter referred to as a specific surfactant as appropriate) is a telomerization method (also referred to as a telomer method) or an oligomerization method. It is derived from a fluoroaliphatic compound produced by (also referred to as oligomer method). Regarding the production method of these fluoroaliphatic compounds, for example, “Synthesis and Function of Fluorine Compounds” (Supervision: Nobuo Ishikawa, Issue: CMC Co., 1987), “Chemistry of Organic Fluorines Compounds”. II "(Monograph 187, Ed by Milos Hudricky and Attila E. Pavlath, American Chemical Society 1995). The telomerization method is a method of synthesizing a telomer by radical polymerization of a fluorine-containing vinyl compound such as tetrafluoroethylene using an alkyl halide having a large chain transfer constant such as iodide as a telogen (example in Scheme-1). showed that).

  The obtained terminal iodinated telomer is usually subjected to appropriate terminal chemical modification such as [Scheme 2], and led to a fluoroaliphatic compound. These compounds are further converted into a desired monomer structure as necessary, and used for the production of the specific surfactant of the present invention.

  As a specific example of the compound produced by the above telomer method, suitable as a fluoroaliphatic compound led to the side chain in the specific surfactant of the present invention, for example, sold by Daikin Chemicals Sales Co., Ltd., Fluorine-based chemical products A-1110, A-1210, A-1310, A-1420, A-1620, A-1820, A-2020, A-1260, A-1460, A-1660, A-1860, A- 1435, A-1635, A-1835, A-1473, A-1637, A-1837, A-1514, A-3420, A-3620, A-3820, A-4020, A-3260, A-3460, A-3660, A-3860, A-3637, A-3837, A-5210, A-5410, A-5610, A-5810, A-7110, A-72 0, A-7310, A-9221, C-1100, C-1200, C-1300, C-1400, C-1500, C-1600, C-1700, C-1800, C-1900, C-2000, C-5200, C-5400, C-5600, C-5800, C-5208, C-5408, C-5608, C-6008, C-8200, C-8300, C-8500, C-9221, C- 8208, C-8308, C-8508, C-9216, E-1430, E-1630, E-1830, E-2030, E-3430, E-3630, E-3830, E-4030, E-5244, E-5444, E-5644, E-5844, F-1420, F-1620, F-1820, F-2020, I-1200, I-1300, I-1400, I 1600, I-1700, I-1800, I-2000, I-1420, I-1620, I-1820, I-2020, I-3200, I-3400, I-3600, I-3800, I-4000, I-3620, I-3820, I-4020, I-5200, I-5400, I-5600, I-8208, I-8207, I-8407, I-8607, M-1110, M-1210, M- 1420, M-1620, M-1820, M-2020, M-3420, M-3620, M-3820, M-4020, M-3433, M-3633, M-3833, M-4033, M-5210, M-5410, M-5610, M-5810, M-6010, M-7210, M-7310, R-1110, R-1210, R-1420, R-1620 , R-1820, R-2020, R-1433, R-1633, R-1833, R-3420, R-3620, R-3820, R-4020, R-3433, R-5210, R-5410, R -5610, R-5810, 6010, R-7210, R-7310, U-1310, U-1710, and CHEMINOX FA, FA-M, FAAC, FAAC-M manufactured by Nippon Mektron Co., Ltd. , FAMAC, FAMAC-M, etc., and the structure of the main component of these fluorine-based chemical products is represented by the following general formula TM-1 (wherein n is an integer of 0 to 20).

  These fluorine-based chemical products are prepared by methods known to those skilled in the art from polymer compound portions having fluoroaliphatic groups in the side chains (of the surfactants having fluoroaliphatic groups in the side chains, fluoroaliphatic groups To a polymer portion having In the above general formula TM-1, the compound represented by -Z below has an acryloyl group or a methacryloyl group at the molecular end, so that a polymer compound portion having a fluoroaliphatic group can be obtained particularly easily by vinyl polymerization. Is particularly preferable.

  In addition, the polymer compound part itself having a fluoroaliphatic group in the side chain using a fluorine-based chemical product obtained by the telomerization method preferably used in the present invention is also a general name “perfluoroalkyl-containing oligomer”. Already commercially available, it can be preferably used. Examples of such chemical products are MEGAFACCF-178K, MEGAFAC F-470, MEGAFAC F-473, MEGAFAC F-475, MEGAFAC F-476, MEGAFAC F manufactured and sold by Dainippon Ink and Chemicals, Inc. -472, MEGAFAC R-08, SURFLON S-381, S-383, S-393, S-101, S-105. Manufactured by Asahi Glass Co., Ltd. Etc. Among these, MEGAFAC F-178K (hereinafter referred to as P-1), MEGAFAC F-470 (hereinafter referred to as P-2), MEGAFAC F-473 (hereinafter referred to as P-3), MEGAFAC F-475 (hereinafter referred to as P-1). -4), MEGAFAC F-476 (hereinafter referred to as P-5), and MEGAFAC F-472 (hereinafter referred to as P-6) are particularly preferred from the viewpoint of suppressing film defects during high-speed coating.

  In the present invention, as the fluoroaliphatic compound led to the fluoroaliphatic group of the specific surfactant, a fluoroaliphatic compound produced by an oligomerization method is also preferable. The oligomerization method is a method of producing an oligomer by cationic polymerization of tetrafluoroethylene in a polar solvent such as diglyme using potassium fluoride or cesium fluoride as a catalyst (Scheme 3), which is the same as the telomer method described above. By using a reactive group (unsaturated bond) or the like in the oligomer obtained by polymerization, it can be led to a polymer compound portion having a fluoroaliphatic group in the side chain through appropriate chemical modification.

  Typical methods for producing a fluoroaliphatic compound other than the telomerization method and the oligomerization method include an electrolytic fluorination method and an indirect fluorination method. In particular, perfluorooctyl sulfonic acid fluoride (Scheme 4) by electrolysis fluorination method and fluorine-based chemical products derived therefrom have been very successful commercially, and have been favorably used in the past. . Instead of this, the present inventors have found that a favorable result can be obtained when a fluorine-based chemical product produced by a telomerization method or an oligomerization method is used.

  The working principle of this effect of the present invention is not clear. The telomerization method and the oligomerization method of the present invention are in contrast to the fluorination of the C—H bond using an aliphatic compound corresponding to electrolytic fluorination and indirect fluorination as a raw material. Polymerization of the fluorinated olefin yields a fluoroaliphatic compound, which may induce favorable results for some reason. In addition, some of the fluorinated chemical products produced by the electrolytic fluorination method that has been favorably used in the past are substances that have low biodegradability and high bioaccumulation. There is concern about toxicity and developmental toxicity. It can be said that it is also an industrial advantage that the fluorine-based chemical product by the telomerization method of the present invention is a substance with higher environmental safety.

  The present inventors have also found that, as another requirement for the fluoroaliphatic group used in the side chain of the present invention, the group represented by the general formula (I) exhibits very good performance.

In general formula (I), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents a single bond or a divalent linking group, and m represents 0 or more. An integer, n represents an integer of 1 or more.

In the general formula (I), specific examples of the alkyl group represented by R ² and R ³ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like. Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. X represents a covalent bond or a divalent linking group (organic group) for binding to the polymer main chain. Preferred X represents —O—, —S—, —N (R ⁴ ) —, —CO—, and is bonded to the polymer main chain directly or via a divalent linking group. Here, R ⁴ represents a hydrogen atom or a C1-C4 alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group, with a hydrogen atom and a methyl group being preferred. X may be any of the above, but —O— is more preferable. m is an integer of 0 or more, preferably an integer of 2 to 8, and particularly preferably m = 2. When m is 2 or more, functional groups on adjacent carbons may be bonded to form an aliphatic ring. n represents an integer of 1 or more, and an integer of 1 to 10 is preferable. Here, n is particularly preferably 2-6.

  The specific surfactant of the present invention has, for example, a polymer compound portion having a fluoroaliphatic group in the side chain represented by the formula (1B).

In the above formula, the definitions of R ² , R ³ , X, m, and n are as described in formula (I), and Y represents a polymer main chain.
A more specific method for producing the polymer compound portion having a fluoroaliphatic group represented by the above formula (1B) will be described.
Specific forms of the polymer compound part include acrylic resin, methacrylic resin, styryl resin, polyester resin, polyurethane resin, polycarbonate resin, polyamide resin, polyacetal resin, phenol / formaldehyde condensation resin, polyvinylphenol resin, polyvinylphenol resin, Examples thereof include those derived from maleic anhydride / α-olefin resin, α-hetero-substituted methacrylic resin and the like. Among them, acrylic resins, methacrylic resins, styryl resins, polyester resins, and polyurethane resins are useful, and acrylic resins, methacrylic resins, and polyurethane resins are particularly useful. These resins can be easily obtained by methods known to those skilled in the art, such as condensation polymerization, addition polymerization, and ring-opening polymerization, using an appropriate polymerizable monomer. The following are examples of acrylic resin and methacrylic resin type fluoroaliphatic group-containing polymer compounds that are most useful and excellent in polymer production suitability.

  A preferred embodiment of the acrylic resin-type fluoroaliphatic group-containing polymer compound portion used in the present invention is one having a structural unit represented by the following general formula (II) as a copolymer unit.

In the formula, R ¹ is a hydrogen atom, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom) or a methyl group which may have a substituent, Y ⁰ is a divalent organic group, X, R ² , R ³ , m, and n have the same meaning as in general formula (I). As Y ⁰ , specific examples of the divalent organic group similar to those of X described above can be given.
Examples of specific structures of the fluoroaliphatic group monomer of the general formula (II) used in the present invention are shown below.
Specific example of n = 4

  Specific example of n = 3

  Specific example of n = 5

  Specific example of n = 6

  The specific surfactant of the present invention can be produced by combining the above-described fluoroaliphatic group-containing polymer part and other groups, and more specifically, the above-described single unit for producing the fluoroaliphatic group. It can be produced by copolymerizing a monomer and another monomer. For example, the fluoroaliphatic group-containing polymer compound portion of the present invention (formula (1B)) is preferably used as a copolymer with a monomer having a polyoxyalkylene group from the viewpoint of coated surface uniformity. .

  Examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene / oxypropylene) random copolymer group, and a poly (oxyethylene / oxypropylene) block copolymer group. It is done. Specific examples of these oxyalkylene groups include those described in JP-A-62-170950, JP-A-62-226143, JP-A-3-17249, and JP-A-8-15858. I can give you. In order to sufficiently achieve the object of the present invention, the molecular weight of the polyoxyalkylene group is preferably 500 to 3,000. The content of the monomer having a polyoxyalkylene group is preferably 10 mol% or more with respect to all monomers for producing the surfactant having the fluoroaliphatic group in the side chain of the present invention. .

Moreover, the monomer for manufacturing the specific surfactant of the present invention described above can be copolymerized with a monomer having an acidic hydrogen atom. As the group having an acidic hydrogen atom, for example, any of a carboxyl group, a phenolic hydroxyl group and known acidic groups in the literature can be used. Known literatures on acidic groups include J. Org. A. Dean ed. , Lange's Handbook of Chemistry 3rd. ed. 1985 McGraw-Hill Book Co. Can give.
Moreover, what is represented by following (A1)-(A7) can be mention | raise | lifted as a concrete thing of the partial structure of the acidic group which the acidic hydrogen atom couple | bonded with the nitrogen atom among these acidic groups.

—SO ₂ NH ₂ (A1)
—SO ₂ NH— (A2)
—CONHSO ₂ — (A3)
-CONHCO- (A4)
—SO ₂ NH—SO ₂ — (A5)
—CONHSO ₂ NH— (A6)
—NHCONHSO ₂ — (A7)

  In addition, acidic groups described in JP-A-8-15858 are also useful. A nitrogen atom-containing heterocyclic structure having a coupler structure described in JP-A-7-248628 is also included. Examples of these nitrogen-containing heterocyclic structures include those represented by the following (H) and (I).

Similarly, an acidic group having a hydrogen atom bonded to a carbon atom adjacent to the electron withdrawing group described in JP-A-2000-19724 is also useful.
In addition, JP-A-11-352681, JP-A-11-327142, JP-A-11-327131, JP-A-11-327126, JP-A-10-339948, JP-A-10-207052, JP-A-10-186642, JP-A-10-161303 Application to the described copolymers is also suitable.

  As the monomer having an acidic hydrogen atom, a vinyl monomer having an unsaturated group capable of radical polymerization is used. Among these vinyl monomers, preferred are acrylate, methacrylate, acrylamide, methacrylamide, styrene, and vinyl. Examples of preferred structures include compounds described in JP-A-10-142778.

  The content of the monomer having an acidic hydrogen atom is 0 to 50 mol%, preferably 0 to 40 mol%, more preferably based on all monomers for producing the specific surfactant according to the present invention. Is 0-30 mol%.

Further, as other copolymerization component, a monomer having a bridge bond described in JP-A-4-222805, an aliphatic group having 9 or more carbon atoms described in JP-A-10-142778, or two or more Copolymerization with an acrylate, methacrylate, acrylamide, or methacrylamide monomer having an aromatic group substituted with an aliphatic group having a carbon atom in the side chain is also suitable.
Further, the present invention is applied to urethane polymer technology described in JP-A-10-186640, JP-A-10-186641, JP-A-2000-3032, JP-A-2000-3040, etc., and disclosed in JP-A-11-327129. Application to polycondensation and polyaddition polymers as described above is also possible. Furthermore, the present invention can also be applied to (meth) acrylate monomers having 2 to 3 perfluoroalkyl groups of 3 to 20 in the molecule described in JP-A-2000-187318.

  The specific surfactant of the present invention can be produced by a known and conventional method. For example, (meth) acrylate having a fluoroaliphatic group, (meth) acrylate having a polyoxyalkylene group, and an acidic group-containing vinyl monomer bonded to an acidic hydrogen atom or nitrogen atom, in an organic solvent, general-purpose radical polymerization It can manufacture by adding an initiator and carrying out thermal polymerization. Alternatively, other addition-polymerizable unsaturated compounds can be added in some cases and produced in the same manner as described above.

  In addition, other addition polymerization unsaturated compounds used in some cases include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley interscience (1975) Chapter 2 Pages 1-483 can be used. Examples of these include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and glycidyl (meth) acrylate, (Meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (Meth) acrylamides such as (p-hydroxyphenyl) -methacrylamide, allyl compounds such as allyl acetate, allyl caproate, allyloxyethanol; ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, o Vinyl ethers such as til vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, phenyl vinyl ether, tolyl vinyl ether, diethylaminoethyl vinyl ether; vinyl acetate, vinyl butyrate, Vinyl esters such as vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl benzoate, vinyl chlorobenzoate: styrene, α-methylstyrene, methylstyrene, dimethylstyrene, chloromethyl Styrene, ethoxymethyl styrene, hydroxy styrene, chlorostyrene Styrenes such as bromostyrene; vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone; olefins such as isobutylene, butadiene and isoprene; other butyl crotonate, dimethyl itaconate, itaconic acid Examples include diethyl, dimethyl maleate, diethyl fumarate, N-vinyl pyrrolidone, N-vinyl pyridine, acrylonitrile and the like.

  Hereinafter, examples of the composition [(P-7) to (P-20)] of the specific surfactant of the present invention and the production method thereof will be shown. In addition, the number in a formula shows the molar ratio of each monomer component.

The method for producing the composition [(P-7) to (P-20)] of the specific surfactant of the present invention will be described below.
Production method of (P-7) After fluorinated chemical product (FM-1, n = 3) produced by telomerization method to acrylic monomer (F-48), radical copolymerization with other components To polymerize.

Production method of (P-8) Fluorine-based chemical product produced by the telomerization method (FM-2, n is a mixture of 3, 4, 5 and 6, n = 3 content 41%, n = 4 The content is 53%) and is led to a methacrylic monomer (F-49), and then polymerized by radical copolymerization together with other components.

Production method of (P-9) After using fluorochemical product (FM-3, n = 4) produced by telomerization method to lead to acrylic monomer (F-50), radical together with other components Polymerize by copolymerization.

Production method of (P-10) After using fluorochemical product (FM-4, n = 3) produced by telomerization method to lead to acrylic monomer (F-51), radical together with other components Polymerize by copolymerization.

Production method of (P-11) After using fluorochemical product (FM-5, n = 4) produced by telomerization method to lead to acrylic monomer (F-52), radical together with other components Polymerize by copolymerization.

Production method of (P-12) After using fluorochemical product (FM-6, n = 3) produced by telomerization method to lead to acrylic monomer (F-53), radical together with other components Polymerize by copolymerization.

Production method of (P-13) Using fluorinated chemical product (FM-7, n = 4) produced by telomerization method, leading to diol (F-54), then other diol, diisocyanate component At the same time, it becomes a urethane polymer by condensation polymerization.

Production method of (P-14) A fluorochemical product (FM-3) produced by the telomerization method is reacted with a cresol / formalin resin to introduce a fluoroaliphatic side chain.

  The content ratio of the fluoroaliphatic group in the surfactant having a fluoroaliphatic group of the present invention is preferably from 10 to 90 mass%, more preferably from 20 to 80 mass%, based on the total weight of the surfactant.

The range of the molecular weight of the surfactant having a fluoroaliphatic group used in the present invention is usually from 3000 to 200,000 as a weight average molecular weight, preferably from 6,000 to 100,000. it can. These molecular weights can be determined by, for example, the GP method using a polystyrene standard substance.
Moreover, the addition amount in the composition of the surfactant which has a fluoro aliphatic group used by this invention is the range of 0.001-10 mass% with respect to all the components except a solvent, More preferably, it is 0.00. It is the range of 01-5 mass%. In addition, two or more of the fluorine-based polymers of the present invention may be used in combination, or may be used in combination with other surfactants.

  Fluoroaliphatic compounds produced by the oligomerization method have a wide distribution when subjected to pyrolysis mass spectrometry, whereas fluoroaliphatic compounds produced by the telomerization method undergo pyrolysis mass spectrometry Since these show a specific distribution, these manufacturing methods can be estimated.

<(A) Color material>
(A) A coloring material means what colors the curable resin composition which concerns on this invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.

As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used.
In addition, the structure includes azo, anthraquinone, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, perylene, diketopyrrolopyrrole, quinophthalone, etc. In addition to organic pigments, various inorganic pigments can also be used.

  Specific examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 4: L, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2. 53: 3, 57, 57: 1, 57: 2, 58: 4, 6.0, 63, 63 :: L, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81 : 2, 81: 3, 81: 4, 83, 88, 90: 1,: 101, 101: 1, 104, 108, 108: 1, 109, 112, 113,: 114, 122,: 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 78, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Specific examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Specific examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI pigment green 7,36.

  Specific examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180, 185.

  Specific examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Specific examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

In addition, when the colored curable resin composition for a color filter of the present invention is a colored curable resin composition for a resin black matrix of a color filter, a black color material can be used as the color material.
As the black color material, a black color material may be used alone or a mixture of red, green, blue and the like may be used. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use them dispersed in an average particle size of 1 gm or less, preferably 0.5 μm or less.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), N0.120 / Lionol Yellow (21090), Dionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D ( 21095), Shimla First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Rio This Ruburu ES (Pigment Blue 15: 6), Rio no-Gen Red GD (Pigment Red 168), Rio Nord Green 2YS (Pigment Green 36), and the like. (Note that the numbers in parentheses above indicate the color index (CI)).

  In addition, specific examples of other pigments that can be used in combination include C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  Specific examples of the black color material that can be used independently include metal particles such as carbon black, acetylene black, lamp black, bone blutter, graphite, iron black, aniline black, cyanine black, titanium black, silver, or metal And particles having the same.

  Examples of preferable metals constituting these metal fine particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium. , Tantalum, bismuth, antimony, and alloys thereof. Further preferable metal is at least one selected from copper, silver, gold, platinum, palladium, tin, calcium, and alloys thereof, and particularly preferable metal is copper, silver, gold, platinum, tin, and alloys thereof. A compound with other elements other than metals is also preferable.

  Examples of the compound of metal and other elements include metal oxides, sulfides, sulfates, carbonates, and the like, and these particles are preferable as the metal compound particles. Of these, sulfide particles are preferred because of their color tone and ease of fine particle formation.

Moreover, a metal, its alloy, and a metal compound may be used together, and 2 or more types may be sufficient as it. Among these, silver or an alloy thereof and a sulfide thereof are particularly preferable because of their high shielding effect. As an example of an alloy, a silver tin alloy is mentioned as a preferable example.
Among these black colorants, carbon black, titanium black, silver, silver tin, and other alloys and sulfides thereof are preferable from the viewpoints of light shielding rate and image characteristics.

Specific examples of preferable carbon black include, for example, the following carbon black.
Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31,

  Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex9O, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550 , Specia1Black350, Specia1Black250, SpecialBlack100, SpecialBlack6, SpecialBlack5, S. specialBlack4, ColorBlack FW1, ColorBlack FW2, ColorBlack FW2V, ColorB1ack FW18, ColorBlack FW200, ColorBlack S160, ColorBlack S170

  Cabot Corporation: Monarchl20, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarchl400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8

  Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven10U, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

  Examples of commercially available titanium black include Mitsubishi Materials Titanium Black 10S, 12S, 13R, 13M, 13M-C, and the like.

  As a method for producing titanium black, a mixture of titanium dioxide and titanium metal is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-20: L610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-20: L6: LO). However, it is not limited to these.

As an example of another black pigment, aniline black, an iron oxide black pigment, and organic pigments of three colors of red, green, and blue can be mixed and used as a black pigment.
In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can also be used as the pigment.

The various pigments described above can be used alone or in combination of two or more.
For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

  The average primary particle size of these pigments is preferably 10 nm to 100 nm, more preferably 10 nm to 50 nm.

The content of the pigment is preferably 30% by mass or more and 70% by mass or less, more preferably 38% by mass or more and 60% by mass or less, and 42% by mass with respect to the total solid content of the colored curable composition. % To 60% by mass is more preferable.
In the curable resin composition according to the present invention, the pigment ratio is preferably 30% by mass or more from the viewpoint of productivity, and 70% by mass or less is preferable from the viewpoint of the contrast performance of the color filter.
In the present invention, the “total solid amount” means all components excluding the solvent component, that is, at least one selected from the group consisting of (a) a colorant, (c) a polymerizable monomer, and a binder resin. d) A photopolymerization initiator, (e) a specific surfactant, and other components other than the solvent.

As described above, a pigment is preferable as a colorant from the viewpoint of heat resistance, light resistance and the like, but a dye can also be used.
Examples of the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Specific examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Specific examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  In addition, examples of phthalocyanine dyes include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic blue 9 etc. are mentioned. Examples of quinoline dyes include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I, Disperse Yellow 64, and the like. Examples of nitro dyes include C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

<(B) Solvent>
(B) The solvent is at least one selected from the group consisting of (a) a coloring material, (c) a polymerizable monomer and a binder resin described later in the curable resin composition according to the present invention, and (d) photopolymerization start. It functions to dissolve or disperse agents and adjust the viscosity.

  (B) As a solvent, glycol ethers and / or alkoxyesters are mentioned, for example. Specific examples of glycol ethers include, for example, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene Glycol acetate, ethylene glycol diacetate, ethylene glycol diethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate , Diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, tripropylene glycol methyl ether, among others, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Is preferred.

  Specific examples of the alkoxyesters include, for example, ethyl acetate, methyl isobutyrate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropion Examples include propyl acid, butyl 3-methoxypropionate, butyl acetate, (n, sec, t-) butyl acetate, butyl stearate, ethyl propionate, ethyl benzoate, ethyl orthoformate, ethyl caprylate, propyl acetate, etc. Of these, ethyl 3-ethoxypropionate is preferred.

  In addition, for example, diisopropyl ether, mineral spirit, n-pentane, amyl ether, n-hexane, cyclohexane, diethyl ether, isoprene, ethyl isobutyl ether, n-octane, Barsol # 2, Apco # 18 solvent, diisobutylene, amyl Acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methylnonyl leketone, propyl ether, dodecane, soak solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, amyl chloride, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, benzonitrile, methyl cellosolve Acetate, methyl isoamyl ketone, methyl isobutyl ketone, amyl acetate, amyl formate, bicyclohexyl, dipentene, methoxymethyl pentanol, methyl amyl ketone, methyl isopropyl ketone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, Cyclohexanone, ethyl lactate, propylene glycol, 3-methoxypropionic acid, 3-ethoxy Propionate, diglyme, ethyl carbitol, butyl carbitol, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate and the like.

  The (b) solvent may be used alone or in combination of two or more.

The content of the solvent (b) in the total solid amount in the curable resin composition according to the present invention is appropriately set in the range of usually 50 to 95% by mass, depending on the ratio (concentration) of the total solid amount. More preferably, it is 70-90 mass%, More preferably, it is 75-85 mass%.
(B) When the content of the solvent is 50% by mass or more, it is preferable from the viewpoint of production such as coating property, and when it is 95% by mass or less, it is preferable from the viewpoint of manufacturing of coating film formation.

<(C) At least one selected from the group consisting of a polymerizable monomer and a binder resin>
The colored curable composition of the present invention contains a photopolymerizable polymerizable monomer.
The polymerizable monomer used in the present invention is an addition polymerizable monomer having at least one ethylenically unsaturated double bond, and a compound having at least one, preferably three or more terminal ethylenically unsaturated bonds in one molecule. Chosen from. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention.

These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.
Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.

Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used.
Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate Sorbitol tetritaconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

Formula ^{_{(A): CH 2 = C}} (R 4) COOCH 2 CH (R 5) OH
In general formula (A), R ⁴ and R ⁵ represent H or CH ₃ .

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; finger ring types such as cyclohexane diisocyanate and isophorone diisocyanate Diisocyanate; aromatic diisocyanate such as toluene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3-hydroxy (1, Reaction products with (meth) acryloyl group-containing hydroxy compounds such as 1,1-trimethacryloyloxymethyl) propane And the like.
In the present invention, the term “(meth) acryloyl group” means that both an acryloyl group and a methacryloyl group are included, and (meth) acrylate, (meth) acrylic acid and the like have the same meaning.

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, A highly sensitive photopolymerizable colored curable composition can be obtained.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  About these polymerizable monomers, the details of usage, such as the structure, single use or combined use, and addition amount, can be arbitrarily set according to the performance design of the final colored curable composition.

The polymerizable monomer is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Moreover, you may introduce | transduce an acid group by making a non-aromatic carboxylic anhydride react with the hydroxyl group of the above-mentioned ethylenic compound as needed.
In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

A preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. In the case of an acid value in this range, the development and dissolution characteristics are excellent, the production and handling are easy, and the photopolymerization performance is good, so that the curability such as the surface smoothness of the pixel is excellent.
Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer are adjusted to fall within the above range. It is desirable to do.

  In the present invention, more preferred polyfunctional monomers having an acid group are mainly dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate which are commercially available as T01382 manufactured by Toa Gosei Co., Ltd. It is a mixture as a component. Other polyfunctional monomers can be used in combination with this polyfunctional monomer.

  Further, in terms of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. In order to increase the strength of the image area, that is, the cured film, the polymerizable compound is preferably a tri- or higher functional compound, and particularly preferably a monomer containing three or more (meth) acryloyl groups in one molecule. .

  Furthermore, it is also effective to adjust both sensitivity and strength by using different functional groups and different polymerizable groups (for example, acrylic ester, methacrylic ester, styrene compound, vinyl ether compound). .

  From the viewpoint of sensitivity, it is preferable to use a monomer containing two or more (meth) acrylate structures, more preferably a monomer containing three or more, and most preferably a monomer containing four or more. . Moreover, it is preferable to contain an EO modified body from a viewpoint of a sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of a sensitivity and an exposure part intensity | strength.

  In addition, selection and use of addition polymerization compounds for compatibility and dispersibility with other components (eg, binder polymer, photopolymerization initiator, colorant (pigment, dye, etc.) in the colored curable composition The method is an important factor, and for example, compatibility may be improved by using a low-purity compound or a combination of two or more types, and also improve the adhesion of the support or the overcoat layer described later. A specific structure may be selected for the purpose.

From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D Le) isocyanurate, pentaerythritol tetraacrylate EO-modified product, dipentaerythritol hexaacrylate EO-modified products thereof as preferred.
Moreover, as a commercial item of a polymerizable monomer, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp Co., Ltd.), DPHA (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH -600, T-600 and AI-600 (manufactured by Kyoeisha) are preferred.

Among these, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetra A modified acrylate EO, a modified dipentaerythritol hexaacrylate EO, and the like are preferable, and at least one selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and pentaerythritol tetraacrylate is more preferable.
As a commercial item, DPHA (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha) are more preferable.

  The content of the polymerizable monomer is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and more preferably 10 to 35% by mass in the total solid content of the colored curable composition in the present invention. More preferably.

Specific examples of the binder resin according to the present invention include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, maleimide and the like. Homopolymers or copolymers containing these monomers, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetylcellulose, novolac resin, resole resin, polyvinylphenol, polyvinyl butyral, etc. JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56. 18 JP, can be used known polymer compounds described in JP-2003-233179 Patent Publication. These may be used alone or in combination of two or more.
In the present invention, when the polymerizable monomer is not contained, the binder resin has at least one polymerizable group.

In the present invention, “(meth) acrylic acid” means that either or both of acrylic acid and methacrylic acid are included, and (meth) acrylate, (meth) acryloyl group, and the like have the same meaning. .
“(Co) polymer” is meant to include both single polymers (homopolymers) and copolymers (copolymers). In the present invention, “acrylic resin” means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic ester having a carboxyl group.

  Among the binder resins, preferred are polymer compounds containing no nitrogen atom, and more preferred is the embodiment (I) or (II) below.

  (I) An alkali-soluble resin having at least one group that promotes alkali solubility (hereinafter abbreviated as “alkali-soluble resin”).

  (II) (A): 5 to 90 mol% of an epoxy group-containing (meth) acrylate, (B): copolymerized with 10 to 95 mol% of another radical polymerizable compound that can be copolymerized with the component (A). (C) Unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group contained in the resulting copolymer, and 10 to 100 mol% of the hydroxyl group produced when the component (C) is added. (D) A resin obtained by adding a polybasic acid anhydride {hereinafter abbreviated as resin (II)}.

In the colored curable composition of the present invention, an alkali-soluble resin can be used as a binder polymer for the purpose of improving film properties.
The alkali-soluble resin used in the present invention is a linear organic polymer, and at least one molecule in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).

More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-25957, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, maleic acid as described in JP-A-59-53836 and JP-A-59-71048 Copolymers, partially esterified maleic acid copolymers, etc., as well as those of acrylic copolymers such as acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group with an acid anhydride added. It is done.
The acid value is preferably in the range of 20 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, more preferably 50 to 150 mgKOH / g.

  As a specific configuration of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include CH ₂ ═C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ Represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ].
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) ) Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms) ), Hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferable. As the polyalkylene oxide chain, a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof can be used, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable.
Examples of the acrylic copolymer having a polyalkylene oxide chain in the side chain include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. , And compounds in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate, etc. An acrylic copolymer as a component.

As the vinyl compound, CH ₂ = CR ¹ R ² [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. . Specific examples include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethylmethacrylate macromonomer, and the like.
Other monomers that can be copolymerized can be used singly or in combination of two or more. Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.

As described above, the acrylic resin preferably has an acid value in the range of 20 to 200 mgKOH / g. When the acid value exceeds 200, the acrylic resin becomes too soluble in alkali and the appropriate development range (development latitude) becomes narrow. On the other hand, if it is too small, such as less than 20, the solubility in alkali is so small that it takes too much time for development, which is not preferable.
In addition, the weight average molecular weight Mw of the acrylic resin (polystyrene conversion value measured by the GPC method) is used to realize a viscosity range that is easy to use in a process such as applying a color resist, and to secure film strength. , Preferably from 2,000 to 100,000, more preferably from 3,000 to 50,000.

In order to improve the crosslinking efficiency of the colored curable composition in the present invention, an alkali-soluble resin having a polymerizable group may be used alone or in combination with an alkali-soluble resin having no polymerizable group.
As the alkali-soluble resin having a polymerizable group, a polymer having an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and further has photocurability and thermosetting properties. Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as each molecule contains an alkali-soluble group such as a COOH group and an OH group and a carbon-carbon unsaturated bond. .

(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin,
(2) an unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule;
(3) Acid pendant type epoxy acrylate resin,
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Of the above, the resins (1) and (2) are particularly preferable.

As a specific example, a copolymer of an OH group, for example, 2-hydroxyethyl acrylate, a COOH group, for example, methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable therewith. Further, a compound obtained by reacting an epoxy ring having reactivity with an OH group and a compound having an unsaturated bond group between carbon (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, in addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group, or an acryloyl group can also be used.
Further, a compound obtained by reacting an unsaturated ring carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyurethane acrylic oligomer, Diamond Shamrock Co., Ltd.). Ltd .; Biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).

  Suitable alkali-soluble resins include, as monomer components, one or more selected from (meth) acrylic acid, maleic acid, maleic anhydride, and crotonic acid, methyl (meth) acrylate, butyl (meth) acrylate, and phenyl (meth) And a copolymer having at least one selected from acrylate, benzyl (meth) acrylate, and styrene.

  As addition amount of alkali-soluble resin, it is preferable that it is the range of 3-70 mass% in the total solid amount of the colored curable composition of this invention, and 5-60 mass% is more preferable.

In preparing the resist, it is preferable to add the following epoxy resin in addition to the alkali-soluble resin. The epoxy resin is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( As described above, manufactured by Tohto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103 etc. In addition, bisphenol F type and bisphenol S type epoxy resins similar to these can also be used.
Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used. Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Tohto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei), and biphenyl type Examples of alicyclic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT. -401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. (manufactured by Toto Kasei), Epilon 430, 673, 695, 850S, 4032 (Dainippon Ink) It can be mentioned. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine-type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resins can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient and the reliability is poor or the flatness is poor.
Specific compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl- 4,4 'diglycidyl biphenyl, ceroxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, etc. are mentioned.

  Resin (II) component (A): 5 to 90 mol% of epoxy group-containing (meth) acrylate, (B): copolymerized with 10 to 95 mol% of other radical polymerizable compound that can be copolymerized with component (A) (C) an unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group contained in the resulting copolymer, and 10 to 100 of the hydroxyl group produced when the component (C) is added. The resin obtained by adding (D) polybasic acid anhydride to mol% will be described below.

  (A): Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxy Examples thereof include butyl (meth) acrylate glycidyl ether, and glycidyl (meth) acrylate is particularly preferable. These (A) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  (A): Copolymerization ratio of epoxy group-containing (meth) acrylate (copolymerization ratio when copolymerizing (A) component and (B) component to produce a copolymer). ") Is 5 to 90 mol% as described above, preferably 20 to 80 mol%, more preferably 30 to 70 mol%. Within this range, heat resistance and strength are excellent, and the addition amount of the polymerizable component and the alkali-soluble component is sufficient, which is preferable.

  On the other hand, the copolymerization ratio of the other radical polymerizable compound that can be copolymerized with the component (B) :( A) is 10 to 95 mol% as described above, preferably 20 to 80 mol%, and more Preferably it is 30-70 mol%. At this ratio, the addition amount of the polymerizable component and the alkadi-soluble component is sufficient, and the heat resistance and strength are excellent.

  As the other radical polymerizable compound that can be copolymerized with the component (B) :( A), one or more mono (meth) acrylates having a structure represented by the following general formula (1) are used. It is preferable.

In the general formula (1), R ^{4 to} R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and R ¹⁰ and R ¹¹ are each independently Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or may be linked to form a ring. The ring formed by connecting R ¹⁰ and R ¹¹ is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms. )

  In the general formula (1), mono (meth) acrylate having a structure represented by the following formula (2), (3), or (4) is preferable. By introducing these structures into the binder resin, it is possible to increase heat resistance and strength. Of course, these mono (meth) acrylates may be used alone or in combination of two or more.

  As the mono (meth) acrylate having the structure represented by the formula (1), various known ones can be used, and those represented by the following general formula (5) are particularly preferable.

In the general formula (5), R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents the general formula (1).
The content of the mono (meth) acrylate having the structure of the general formula (1) in the copolymerization monomer is usually 5 to 90 mol%, preferably 10 to 70 mol%, and more preferably 15 to 50 mol. %.

  Moreover, although it does not specifically limit as (B) radically polymerizable compound other than the above, The following can be mentioned as the specific example.

Styrene, α-, o-, m-, p-alkyl, nitro, cyano, amido ester derivatives of styrene.
Gens such as butadiene, 2,3-dimethyl-butadiene, isoprene and chloroprene.
Methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid- sec-butyl, (tert) -butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid-2- Ethylhexyl, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, (meth) Isobornyl acrylate, adamantyl (meth) acrylate, (meth) a Allyl acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, (meth ) Salicyl acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, (meta ) Cresyl acrylate, (meth) acrylic acid-1,1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro (meth) acrylate -Iso-propyl, triphenylmethyl (meth) acrylate, (meth ) (Meth) acrylic such as cumyl acrylate, (meth) acrylic acid-3- (N, N-dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl Acid esters.

(Meth) acrylic acid amide, (meth) acrylic acid: ES1N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N -(Meth) acrylic acid amides such as di-iso-propylamide, (meth) acrylic acid anthracenylamide.
Vinyl compounds such as (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate.
Unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate and diethyl itaconate.
Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide.
N- (meth) acryloylphthalimide and the like can be mentioned.

In order to impart more excellent heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the component (B).
In this case, the copolymerization ratio selected from styrene, benzyl (meth) acrylate and monomaleimide is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.

A known solution polymerization method is applied to the copolymerization reaction between the component (A) and the component (B). The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Specific examples thereof include ethyl acetate, Isoaropiru, cellosolve acetate, ethylene glycol monoalkyl ether acetates such as butyl cellosolve acetate; diethylene glycol monomethyl ether acetate, carbitol acetate, diethylene grayed recall monoalkyl ether acetates such as butyl carbitol acetate Propylene glycol monoalkyl ether acetates;
Acetic esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol and butyl carbitol; Triethylene glycol dialkyl ethers; Propylene glycol dialkyl ethers Diether ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as bengan, toluene, xylene, octane and decane; petroleum Petroleum solvents such as ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate Ethers; dimethylformamide, N- methylpyrrolidone and the like.

  These solvents may be used alone or in combination of two or more. The amount of these solvents used is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, with respect to 100 parts by mass of the resulting copolymer. When the amount of the solvent used is within this range, it is easy to control the molecular weight of the copolymer.

The radical photopolymerization initiator used in the copolymerization reaction between the component (A) and the component (B) is not particularly limited as long as it can initiate radical polymerization, and is generally used organic peroxidation. An object or an azo compound can be used.
Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.
Specific examples of the radical photopolymerization initiator include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxide. Oxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2 , 5-Bis (t-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t- Butylcyclohexyl) peroxydicarbonate Diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, laudyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1 , 1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarbonamide and the like, radical light having an appropriate half-life depending on the polymerization temperature One or more polymerization initiators are selectively used.
The amount of the radical photopolymerization initiator used is 0.5 to 20 parts by mass, preferably 1 to 10 parts per 100 parts by mass of the monomer used in the copolymerization reaction, that is, the total of the component (A) and the component (B). Part by mass.

  The copolymerization reaction between the component (A) and the component (B) may be carried out by dissolving the monomer and radical photopolymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring. You may carry out by dripping the monomer which added the polymerization initiator in the solvent which heated and stirred. Further, the monomer may be added dropwise while the radical photopolymerization initiator is added to the solvent and the temperature is raised. The reaction conditions can be freely changed according to the target molecular weight.

(C) component added to the epoxy group contained in the copolymer of (A) component and (B) component is an unsaturated monobasic acid.
(C) As a component, a well-known thing can be used, The unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned, As an example, acrylic acid, methacrylic acid, crotonic acid, o-, Examples thereof include monocarboxylic acids such as m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano substitution. Of these, acrylic acid and / or methacrylic acid are preferred.
These (C) components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

Component (C) is added to 10 to 100 mol% of the epoxy group contained in the copolymer obtained by the copolymerization reaction of component (A) and component (B), preferably 30 to 100 mol%. More preferably, it is added to 50 to 100 mol%. When the addition ratio of the component (C) is within this range, the stability over time is excellent.
As a method for adding the component (C) to the copolymer of the component (A) and the component (B), a known method can be employed.
As the (D) polybasic acid anhydride to be added to the hydroxyl group produced when the (C) component is added to the copolymer of the (A) component and the (B) component, known ones can be used, Dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimedite anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid Examples thereof include polybasic acid anhydrides such as anhydrides and biphenyltetracarboxylic acid anhydrides. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable.
(D) A component may be used individually by 1 type and may be used in mixture of 2 or more types. By adding such components, the Novainder resin used in the present invention can be made alkali-soluble.

  Component (D) is added to 10 to 100 mol% of the hydroxyl group produced when component (C) is added, preferably 20 to 90 mol%, more preferably 30 to 80 mol%. . When the ratio is within this range, the remaining film ratio during development is good and the solubility is sufficient.

  As a method of adding the component (D) to the hydroxyl group produced when the component (C) is added to the copolymer of the component (A) and the component (B), a known method may be adopted. it can.

In the present invention, in order to further improve the photosensitivity, (D) after addition of polybasic acid anhydride, a glycidyl ether compound having a glycidyl (meth) acrylate or a polymerizable unsaturated group in a part of the generated carboxyl group is added. In order to add or improve developability, after adding (D) polybasic acid anhydride, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl group, Both of these may be added.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (manufactured by Nagase Chemical Industries, Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol) EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like.
These resin structures are described in, for example, JP-A-8-297366 and JP-A-2001-89533, and are already known.

As a polystyrene conversion weight average molecular weight (Mw) measured by GPC of such resin (II), 3000-100000 are preferable and 5000-50000 are especially preferable. When the molecular weight is in this range, heat resistance, film strength and solubility are excellent.
The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2.0 to 5.0.

  Binder resin may be used individually by 1 type, and may use 2 or more types together. The ratio of the binder resin is preferably selected in the range of 10 to 80% by mass, particularly preferably 20 to 70% by mass, based on the total solid content in the colored curable composition of the present invention.

  A silane coupling agent can be blended for the purpose of improving the affinity of the interface between the colorant and the binder resin. The ratio of the silane coupling agent is preferably selected in the range of 1 to 10% by mass in the total solid content.

<(D) Photopolymerization initiator>
The colored curable composition of the present invention contains a photopolymerization initiator that directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

When a black photopolymerizable layer is formed with a colored curable composition, the photopolymerization initiator is sensitive to ultraviolet light to visible light because the image is exposed from the photopolymerizable layer through a pattern mask. It means a compound that exhibits, and it is preferable to use an exposure light source corresponding to the image exposure.
Also in the red, green, and blue photopolymerizable layers, red, green, and blue allo-image patterns are formed between the four black matrix patterns by exposure through a pattern mask for each color and other methods. Therefore, as in the case of the black matrix pattern, the photopolymerization initiator is preferably a compound that exhibits sensitivity to ultraviolet light to visible light, particularly a compound that exhibits spectral sensitivity at a wavelength of 450 nm or less, particularly 400 nm or less.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbiimidazoles described in JP-A-10-39503. Derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino-acids such as N-phenyl-glycine, N-aryl-α-amino-acid salts, N-aryl-α-amino-acid esters, etc. Examples include radical activators, α-amino-alkylphenone compounds, and oxime ester initiators described in JP-A No. 2000-80068.

  Furthermore, examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Examples include hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

Listed specific examples of the photopolymerization initiator that can be used in the present invention are described below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Halomethylated triazine derivatives such as ethoxynaphthyl) -4,6-bis (todichloromethyl) mono-s-triazine and 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 4- (o-bromo-pN) , N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (Tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, etc. It is done.

  2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2-benzofuryl) vinyl] -1,3,4-oxadi Azole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  2- (2′-chlorophenyl) -4,5-diphenyl-imidazolol dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (2 '-Fluorophenyl) -4,5-diphenyl-imidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenyl-imidazole dimer, (4'-methoxyphenyl) -4,5 -Imidazole derivatives such as diphenyl-imidazole dimer.

  Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl edel.

  Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone.

  Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone.

  2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl (p-isopropylphenyl) ) Ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p -Acetophenone derivatives such as butylphenyl) ketone.

  Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone.

Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.
Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine.
Phenazine derivatives such as 9,10-dimethylbenzphenazine.
Anthrone derivatives such as benzanthrone.

  Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bisphenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di Cyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, dicyclopentadienyl-Ti-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis2,3 4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dicyclopen Dienyl -Ti-2,6-difluoro-3- (pyrr-1-yl) - titanocene derivatives such as phenyl-1-yl.

  2-Methyl-1 [4- (methyl-thio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 , 2-Benzyl-2-dimethyl-amino-1- (4-morpholinophenyl-) butanone-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopro Piophenone, 2-ethylhexynol-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. [Alpha] -aminoalkylphenone compounds.

  1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- Oxime ester compounds such as 3-yl]-, 1- (O-acetyloxime).

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-mol Forinophenyl) -butanone-1,2,4,6 trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4 -Acetophenone derivatives such as morpholinobyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, Examples thereof include benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl dimethyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, various titanocene compounds described in JP-a-5-83588, such as dicyclopentadienyl -Ti- bis - phenyl, dicyclopentadienyl -Ti- bis-2,6-difluorophen-1-yl, dicyclohexyl pentadienyl -Ti- bis-2,4-di - fluoro phenyl-1-yl, dicyclopentadienyl -Ti- bis-2,4,6-trifluorophen-1-yl, dicyclopenta dienyl -Ti- bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadienyl -Ti- bis-2,3,4,5,6-pentafluoro E d-1-yl, dimethylcyclopentadienyl -Ti- bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl -Ti- bis-2,4,6-trifluoro-phenyl- 1-yl, dimethylcyclopentadienyl -Ti- bis-2,3,5,6-tetrafluorophen-1-yl, dimethylcyclopentadienyl -Ti- bis 2,3,4, 5,6-pentafluoro-phenyl-1-yl, JP-a 1-304453 and JP-iron Hei 1-152109 JP - arene complexes.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like. Specific examples include Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As the photopolymerization initiator (e) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  Specific examples of the photopolymerization initiator component include dialkyl acetophenone compounds described on pages 16 to 26 of "Fine Chemical" (March 1, 1991, vo 1.20, N0.4). Benzoin, thioxanthone derivatives, and the like, as well as hexaarylbiimidazole series, S-trihalomethyltriazine series, and JP-A-4-221958 described in JP-A-58-403023 and JP-B-45-37377. And a combination of a titanocene and a xanthene dye, an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group, and the like described in JP-A-4-219756. .

A photoinitiator may be used individually by 1 type and may use 2 or more types together.
The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to 1% by mass with respect to the total solid content of the colored curable composition. 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

If necessary, the curable resin composition of the present invention can contain a sensitizing dye according to the wavelength of the image exposure light source for the purpose of improving the sensitivity.
Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703, JP-A-5-289335, and the like. A coumarin dye having a complex belly, a 3-ketocoumarin compound described in JP-A-3-239703, JP-A-5-289335 and the like, a pyromethene dye described in JP-A-6-19240, In addition, JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58 -15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57. 168088 JP, may be mentioned JP-A 5-107761, JP-A No. 5-210240, JP-dye having a dialkylamino benzene skeleton are described in, JP-A-4-288818 discloses the like.

  Suitable sensitizing dyes that can be used in the present invention are amino group-containing proliferation dyes, and more preferable are compounds having both an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-bis (dimethylamino) benzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3, Benzophenone compounds such as 3′-diaminobenzophenone and 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- ( p-dimethylaminophenyl) Nzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3 , 4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pydidine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pidimidine, (p P-dialkylaminophenyl group-containing compounds such as -diethylaminophenyl) pyrimidine. Of these, 4,4'-dialkylaminobenzophenone is most preferred.

  The content of the sensitizing dye in the total solid content of the curable resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass. is there.

<Other ingredients>
The colored curable composition of the present invention can contain other components. Other components include, for example, chain transfer agents, thermal polymerization inhibitors, plasticizers, dispersants, dispersion aids, storage stabilizers, surface protective agents, smoothing agents, coating aids, adhesion improvers, and coating properties. Agents, development improvers, silane coupling agents and the like.

(Chain transfer agent)
Examples of the chain transfer agent which can be added to the colored curable composition of the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

(Thermal polymerization inhibitor)
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallool, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like.
The blending amount of these thermal polymerization inhibitors is preferably selected in the range of 0 to 3% by mass with respect to the total solid content in the colored curable composition.

(Plasticizer)
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, todiethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like.
The blending amount of these plasticizers is preferably selected in the range of 0 to 10% by mass with respect to the total solid content in the curable colored resin composition.

(Dispersant)
Examples of the dispersant include polymer dispersants such as acrylic acid and styrene, acrylic acid ester and methacrylic acid, acrylic acid and methacrylic acid ester, styrene and maleic acid, copolymers, amide compounds, urethane compounds, and lactams. Resin-type dispersants such as polyamide-based compounds, barbituric acid-based compounds, polyamide-based compounds and polyurethane-based compounds (commercially available products such as Dischavic 130, Dispersic 161, Dispersic 182 and Dispersic 170, manufactured by BYK Chemie) Efka 46, Efka 47, etc. manufactured by Efka Corporation) can be used.
Among these, a dispersant having a nitrogen-containing functional group is preferable, and an acrylic dispersant, a urethane dispersant, and a graft copolymer dispersant are more preferable.

As an acrylic dispersing agent, an AB block copolymer and / or a BAB block comprising an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base. A copolymer is preferred.
The A block constituting the block copolymer of the acrylic dispersant is a quaternary ammonium base, preferably -N ⁺ R _1a R _2a R _3a · Y ⁻ (where R _1a , R _2a , and R _3a are each Independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R _1a , R _2a , and R _3a are bonded to each other to form a cyclic structure; Y ⁻ represents a counter anion.) And has a quaternary ammonium base. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R _1a R _2a R _3a , as a cyclic structure formed by combining two or more of R _1a , R _2a , and R _3a with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the following are mentioned, for example.

In said formula, R represents either group among R < _1a > -R < _3a >.
These cyclic structures may further have a substituent. As _R 1a _{to R 3a} in the ^{_{-N + R 1a R 2a R 3a}} , and more preferably may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a phenyl group or a benzyl group which may have a substituent.

  As the A block, those containing a partial structure represented by the following general formula (6) are particularly preferable.

In the general formula (6), R _1a , R _2a and R _3a each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R _1a , R _2a , and R _3a may be bonded to each other to form a cyclic structure. R _4a represents a hydrogen atom or a methyl group. X represents a divalent linking group, and Y ⁻ represents a counter anion.

In the general formula (6), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R _5a —, —COO—R _6a — (provided that R _5a and R _6a is a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R _7a —O—R _8a —: R _7a and R _8a are each independently an alkylene group). And the like, and preferably —COO—R _6a —.

Examples of Y ⁻ of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.

Two or more kinds of partial structures containing a specific quaternary ammonium base such as the general formula (6) may be contained in one A block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done.
The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. Most preferably, it is not included in the A block.

  On the other hand, as the B block constituting the block copolymer of the dispersant, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) methacrylate , Isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate (Meth) acrylate monomers such as glycidyl ethyl acrylate and N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, N-methylolacrylamide, , N-dimethyl-acrylamide, (meth) acrylamide monomers such as N, N-dimethylaminoethyl acrylamide; vinyl acetate; acrylonitrile; azyl glycidyl ether, crotonic acid glycidyl ether; N-methacryloylmorpholine Polymer structures.

  The B block is particularly preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (7).

In the general formula (7), R _9a represents a hydrogen atom or a methyl group. R _10a represents a cyclic or chain alkyl group which may have a substituent, an allyl group which may have a substituent, or an aralkyl group which may have a substituent.

Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be.
When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 50% by mass, more preferably 0 to 20% by mass, but it is most preferable that a partial structure other than the (meth) acrylic acid ester monomer is not included in the B block.

The acrylic dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block, and such a block copolymer. Is prepared, for example, by the living polymerization method shown below.
The diving polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical diving polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

  In synthesizing such an acrylic dispersant, JP-A-9-62002 and P.I. Lutz. P. Massoneta]. , Polym. Bull. 12, 79 (1984), B.I. C. Ande: rson, G.M. D. Andrewseta 1, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, etal, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi right hand, Koichi Hatada, polymer processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawaki, Polymer Journal, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W .; R. Known methods described in, for example, Hertierta 1, Macromolecules, 20, 1473 (1987) can be employed.

  Whether the dispersant used in the present invention is an AB block copolymer or a B-A-B block copolymer, the A block / B block ratio (mass ratio) constituting the copolymer. Is usually in the range of 1/99 or more, especially 5/95 or more, and usually 80/20 or less, especially 60/40 or less. Outside this range, it may not be possible to combine good heat resistance and dispersibility.

Further, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the B-A-B block copolymer according to the present invention is usually preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.
Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mg-KOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and expressing it in mg of KOH corresponding to the acid value.

  Moreover, although the acid value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, it is generally preferable that the acid value is low, and is usually 100 mg-KOH / g or less, and its molecular weight is The weight average molecular weight (Mw) in terms of polystyrene measured by GPC is usually in the range of 1000 or more and 100,000 or less. When the molecular weight of the block copolymer is too small, the dispersion stability is lowered, and when it is too large, the developability and the resolution tend to be lowered.

In the present invention, as the dispersant, a commercially available urethane-based and / or acrylic-based dispersant having a structure similar to that described above can also be applied.
Examples of urethane dispersants include (1) polyisocyanate compounds, (2) compounds having one or two hydroxyl groups in the same molecule, and (3) compounds having active hydrogen and tertiary amino groups in the same molecule. A dispersion resin obtained by reacting is preferable.

(1) Polyisocyanate compound Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-didiphenylmethane diisocyanate, naphthalene-1,5-diisocyanate. , Aromatic diisocyanates such as tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) ), Alicyclic diisocyanates such as ω, ω′-diisocyne trimethylcyclohexane, xylylene diisocyanate, α, an aliphatic diisocyanate having an aromatic ring such as α, α ′, α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, Todiisocyanates such as 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyols thereof Examples include adducts.

  Preferred as the polydiisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used individually by 1 type, and may mix and use 2 or more types.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. For example, a method of obtaining a desired isocyanurate group-containing polyisocyanate by performing trimerization and stopping the trimerization by adding a catalyst poison, and then removing the polyisocyanate at the end reaction by solvent extraction and thin-film distillation.

(2) Compounds having one or two hydroxyl groups in the same molecule Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and these compounds. And a mixture of two or more of these having one end hydroxyl group alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these.
Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.
Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxydetramethylene) adipate.

  Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propane-diol, 2-methyl-2-propyl-1,3-propane-diol, 2-butyl-2-ethyl-1,3-propane-diol, 1,5-pentane Diol, 1,6-hexanediol, 2-methyl-2 4-pentanediol, 2,2,4-trimethyl - 1, 3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene Glycol, aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromas such as xylylene glycol and bishydroxyethoxybenzene Group glycol, N-alkyl dialkanolamine such as N-methyl-diethanolamine), such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc. Diols or carbon number 1-2 And polylactone diol or polylactone monool obtained by using a monohydric alcohol of No. 5 as an initiator, such as polycaprolactone glycol, polymethylvalerolactone, and a mixture of two or more thereof.

  Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. .

Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.
Of the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred.

  The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

(3) Compound having active hydrogen and tertiary amino group in the same molecule The compound having active hydrogen and tertiary amino group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl 1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1, 4-butanediamine and the like can be mentioned.

  In addition, as the tertiary amino group is a nitrogen-containing heterocycle, 4-pyrazole ring, imidazole ring, todiazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazonole ring N-containing hetero 5-membered rings such as benzothiazole ring and benzothiadiazole ring, and nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinidine ring, acridine ring and isoquinoline ring. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. .
Further, specific examples of the compound having a todiazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 2,4-todiazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3 triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.

  A preferable blending ratio of the urethane-based dispersant raw material is 10 to 200 parts by mass of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. Is 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass. .

  The polystyrene-converted weight average molecular weight (Mw) measured by GPC of such a urethane-based dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. Range. Within this molecular weight range, the dispersibility and dispersion stability are excellent, the solubility and dispersibility are excellent, and at the same time, the reaction is easily controlled.

The production of such a urethane-based dispersant is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl One or more of aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.
In the production, a usual urethanization reaction catalyst is used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned.

The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mg-KOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value by neutralizing and titrating a basic group with an acid. If the amine value is lower than the above range, the dispersing ability tends to be lowered, and if it exceeds the above range, the developability tends to be lowered.
In addition, when an isocyanate group remains in the dispersion resin obtained by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability with time of the product becomes high.

  As the graft copolymer dispersant, those having a repeating unit containing a nitrogen atom in the main chain are preferable. Especially, it is preferable to have a repeating unit represented by the following general formula (8) or / and a repeating unit represented by Formula (9).

In General Formula (8), R ¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any of the following General Formulas (10) to (12).

In the general formula (8), R ¹ represents a chain-like or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene, or propylene, preferably 2 to 3 carbon atoms, more preferably. Ethylene group. A represents a hydrogen atom or any one of the following general formulas (10) to (12), and is preferably general formula (10).

In said general formula (9), R < ¹ >, A is synonymous with R < ¹ >, A of General formula (8).

In the general formula (10), W ₁ represents a leather-bound or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, and hexylene is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the general formula (11), Y ₁ represents a divalent linking group. Also preferred are alkylene groups having 1 to 4 carbon atoms such as ethylene and propylene, and alkyleneoxy groups having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy.
W ₂ represents a bottomed or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, butylene, etc. Among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable.
Y ₂ represents a hydrogen atom or —CO—R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms such as ethyl-, propyl, butyl, pentyl, hexyl, etc., among which carbon number such as ethyl, propyl, butyl, pentyl, etc. 2-5 alkyl groups are preferred).
q represents the integer of 1-20, Preferably it is an integer of 5-10.

In the general formula (12), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, and in particular, an alkyl group having 10 to 20 carbon atoms such as stearyl. A hydroxyalkyl group having 10 to 20 carbon atoms and having 1 to 2 hydroxyl groups such as monohydroxystearyl is preferable.

The content of the repeating unit represented by formula (8) or (9) in the graft copolymer of the present invention is preferably as high as possible, usually 50 mol% or more, and preferably 70 mol% or more. The repeating unit represented by the general formula (8) and the repeating unit represented by the general formula (9) may both be present, and the content ratio is not particularly limited, but the general formula ( It is preferable that the repeating unit 8) is contained in a larger amount.
The total number of repeating units represented by general formula (8) or general formula (9) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50.

Moreover, repeating units other than general formula (8) and general formula (9) may be included, and as other repeating units, an alkylene group, an alkyleneoxy group, etc. can be illustrated, for example. The graft copolymer of the present invention preferably has a terminal having —NH ₂ and —R ₁ —NH ₂ (R ₁ is as defined above for R ₁ ).
In the graft copolymer of the present invention, the main chain may be linear or branched.

  The amine value of the graft copolymer of the present invention is usually from 5 to 100 mgKOH / g, preferably from 10 to 70 mgKOH / g, and more preferably from 15 to 40 mgKOH / g. When the amine value is within this range, the dispersion stability is good, the viscosity is stable, the residual liquid is reduced, and the electrical characteristics after the liquid crystal panel is formed are also improved.

  As a weight average molecular weight measured by GPC of the said dispersing agent, 3,000-100,000 are preferable and 5,000-50,000 are especially preferable. When the weight average molecular weight is within this range, aggregation of the colorant can be prevented, the viscosity itself is not too high, and the solubility in an organic solvent is good.

  As a method for synthesizing the dispersing agent, a known method can be employed. For example, a method described in JP-B-63-30057 can be used.

The said dispersing agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
The blending amount of the dispersant is preferably selected in the range of 0 to 30% by mass with respect to the total solid content in the colored curable composition.
Moreover, in the colored curable composition for color filters of the present invention, the content of the dispersant is usually 10 to 300% by mass, preferably 20 to 100% by mass, and particularly preferably based on the colorant. 30 to 80% by mass. When the content of the dispersing agent is within this range, aggregation can be prevented, the film thickness becomes an appropriate thickness, and when used in a color filter, cell gap control failure in the liquid crystal cell forming process is suppressed. It is possible.

  The colored curable composition in the present invention may be used in combination with a conventionally known dispersant (pigment dispersant) shown below in addition to the polymer dispersant.

Known dispersants (pigment dispersants) include polymer dispersants [for example, polyamidoamines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic types. Copolymers], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of known dispersants (pigment dispersants) that can be used in the present invention include "Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 161, 162, 163, 164, 165, 166" manufactured by BYK Chemie. , 170 (polymer copolymer) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide) manufactured by EFKA ), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Ajisper PB821, PB822 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd., Poly Low No. 50E, No. 300 (acrylic copolymer) ”,“ Dispalon # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ”manufactured by Enomoto Kasei Co., Ltd.,“ “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)”, “acetamine 86 (stearylamine acetate)”, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester) manufactured by Lubrizol Corporation Amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate) "manufactured by Nikko Chemical Co., Ltd. , M YS-IEX (polyoxyethylene monostearate) ”and the like.

  In the present invention, when a known dispersant as described above is used, with respect to the compound having the acid value of 20 to 300 mg / g and the weight average molecular weight in the range of 3,000 to 100,000, It can be used in the range of 10 to 100% by mass, that is, 1/10 to 1/1 (equal amount).

(Dispersing aid)
Examples of the dispersion aid include pigment derivatives.
As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine And derivatives such as pigments.

  As the substituent of the pigment derivative, a sulfonic acid group, a sulponamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. are directly on the pigment skeleton or an alkyl group, an aryl group, a hetero belly Examples thereof include those bonded via a group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, these substituents may be substituted by a plurality of pigment skeletons, or may be a mixture of compounds having different substitutions.

  Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of anthraquinone pigments, sulphonic acid derivatives of quinacridone pigments, and sulfonic acids of diketopyrrolopyrrole pigments. And sulfonic acid derivatives of dioxazine pigments.

  Examples of commercially available pigment derivatives include azo-based Solvase 22000 manufactured by Avicia, phthalocyanine-based Solsperse 5000, and Fuka 475 manufactured by Fuka. These pigment derivatives may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The blending amount of the dispersion aid is preferably selected in the range of 0 to 20% by mass with respect to the total solid content in the colored curable composition.

(Silane coupling agent)
Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-amino Propyltriethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.

  In addition to the above, as specific examples of additives that can be used in the colored curable resin composition of the present invention, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, Alkali-soluble resins such as partially esterified maleic acid copolymers, acidic cellulose derivatives, hydroxyl group-added polymers with acid anhydrides, alcohol-soluble nylon, phenoxy resins formed from bisphenol A and epichlorohydrin; Etc.

  Examples of other additives include EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), disperse aid 6, dis Polymer dispersing agents such as Perth Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by Sannopco); various sparse dispersions such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 Agent (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.); UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; And an aggregation inhibitor such as sodium polyacrylate.

  Further, when the alkali solubility of the uncured part is promoted and the developability of the photocurable composition is further improved, the photocurable composition is an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

[Method for producing curable resin composition of the present invention]
Next, a method for preparing the curable resin composition for a color filter according to the present invention will be described.
First, (a) the color material and (b) the solvent are weighed in predetermined amounts, and in the dispersion treatment step, (b) the color material is dispersed in the solvent and the liquid hatching resin composition (ink-like material) is obtained. ). In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By this dispersion treatment, the color material (a) is finely divided, so that the coating characteristics of the curable resin composition are improved, and a color filter with improved transmittance of transmitted light is obtained.

(B) When (a) the colorant is dispersed in the solvent, it is preferable that (c) a binder resin and / or a monomer, a dispersant, a dispersion aid, and the like be used in combination as appropriate. In particular, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time. For example, when the dispersion treatment is performed using sandgrawing, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several millimeters.
The temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably room temperature to 80 ° C. The dispersion time varies depending on the composition of the ink-like material {colorant, solvent, dispersant, dispersion aid}, the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted as appropriate.
.

  A binder resin and / or a monomer, a polymerizable compound, a photopolymerization initiator, and other components are mixed with the ink-like material obtained by the dispersion treatment step to obtain a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and mixing, since a fine dust may mix, it is preferable to filter the obtained ink-like thing with a filter etc.

In the colored curable composition of the present invention, the ratio (concentration) of the total solid content in the entire colored curable composition is preferably 2 to 50% by mass. More preferred is 8 to 30% by mass, and particularly preferred is 12 to 25% by mass.
If the ratio of the total solid amount is too large, application stripes are likely to occur, which is not preferable. When the ratio of the total solid amount is too small, the viscosity is lowered, the colored curable composition flows during drying, and drying unevenness and dent defects are generated, which is not preferable.

  In particular, when producing a color filter having a thin coating film thickness after drying, the ratio of the total solid amount is usually 30% by mass or less, preferably 20% by mass or less, more preferably 18% by mass or less, and particularly preferably. Is less than 16% by mass, usually 2% by mass or more, preferably 4% by mass or more, and more preferably 8% by mass or more.

  On the other hand, particularly when a color filter having a thick coating film thickness after drying is produced, the ratio of the total solid amount is usually 8% by mass or more, preferably 10% by mass or more, and more preferably 12% by mass or more. Particularly preferably, it is 14% by mass or more, usually 30% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.

<Coloring Pattern Forming Method, Color Filter Manufacturing Method, and Color Filter>
Next, the colored pattern forming method, the color filter manufacturing method, and the color filter of the present invention will be described.
The colored pattern forming method of the present invention includes a step of applying the colored pattern forming composition of the present invention by a slit coating method at a coating speed of 200 mm / sec to 400 / sec mm, thereby forming a desired colored pattern. Can do. Since the composition for forming a colored pattern of the present invention has predetermined physical properties, even when slit coating is performed at a coating speed of 200 mm / sec to 400 / sec mm, there is little coating unevenness and occurrence of coating defects. It is possible to form a photosensitive film with no defects and high efficiency.
This colored pattern forming method is preferably applied to a method for producing a color filter.
Hereinafter, a color filter manufacturing method (a color filter manufacturing method of the present invention) to which the colored pattern forming method of the present invention is applied will be described.

The method for producing a color filter of the present invention comprises a step of forming a photosensitive film by applying the colored curable resin composition of the present invention directly or via another layer (hereinafter referred to as “photosensitive film” as appropriate). Abbreviated as “formation step”), a step of pattern exposure (exposed through a mask) of the formed photosensitive film (hereinafter abbreviated as “exposure step” as appropriate), and photosensitivity after exposure. A step of developing the film to form a colored pattern (hereinafter abbreviated as “development step” as appropriate).
Hereafter, each process in the manufacturing method of this invention is demonstrated.

(Photosensitive film forming process)
In the photosensitive film forming step, the colored film forming composition of the present invention is applied (applied) directly or on a substrate having another layer to form a photosensitive film.

Examples of the substrate that can be used in this step include soda glass, Pyrex (registered trademark) glass, quartz glass, and those in which a transparent conductive film is attached to these substrates, photoelectric sensors used for imaging devices, and the like. Examples of the conversion element substrate include a silicone substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, if necessary, an undercoat layer (other layers) may be provided on these substrates for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the substrate surface.

In the method for producing a color filter of the present invention, the method for coating the colored pattern forming composition of the present invention on a substrate includes a step of coating at a coating speed of 200 mm / sec to 400 / sec mm using a slit coating method. It takes a thing. According to the colored pattern forming composition of the present invention, a uniform photosensitive film free from coating defects can be formed with high productivity by such high-speed slit coating, and therefore, when used in the method for producing a color filter of the present invention. Although the effect is remarkable, it goes without saying that the photosensitive film can be formed by applying various coating methods such as an inkjet method, spin coating, cast coating, roll coating, and screen printing.
As a coating film thickness of a colored curable resin composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is still more preferable.

  The photosensitive film coated on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven, or the like.

(Exposure process)
In the exposure step, the photosensitive film formed in the photosensitive film forming step is exposed through a mask having a predetermined mask pattern, that is, pattern exposure is performed.
In this step, only the coating film portion irradiated with light can be cured by exposing the photosensitive film as the coating film through a predetermined mask pattern.

As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.
If the color filter to be manufactured is a liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter to be manufactured is a solid-state imaging device, it is more preferably preferably 50~1000mJ / cm ² 30~1500mJ / cm ² within the above range, and most preferably 80~500mJ / cm ^2.

(Development process)
Next, by performing development processing, the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains. Any developer can be used as long as it dissolves the film of the photocurable composition in the uncured part while not dissolving the cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

As said organic solvent, the above-mentioned solvent which can be used when preparing the colored curable resin composition of this invention is mentioned.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution diluted with pure water so as to be 1% by mass is preferably used as the developer.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

After the development step, excess developer is washed away and dried, followed by heat treatment (post-bake).
The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicone substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the coating film after development is in the above-mentioned condition. be able to.

  By repeating the photosensitive film formation step, the exposure step, and the development step (and heat treatment if necessary) as described above for the desired number of hues, a color filter having the desired hue (the color filter of the present invention) is produced. Is done.

The color filter obtained by the method for producing the color filter of the present invention as described above has a structure having a colored pattern formed on the substrate using the colored curable resin composition of the present invention. Was as high as 5000 or more.
Here, the contrast means a contrast that is individually evaluated for each color of R (red), G (green), and B (blue) constituting the color filter.
The contrast measurement method is as follows. In the state where the polarizing plates are overlapped on both sides of the object to be measured and the polarizing directions of the polarizing plates are parallel to each other, the backlight Y is applied from the side of one polarizing plate, and the luminance Y1 of the light passing through the other polarizing plate is obtained. taking measurement. Next, in a state where the polarizing plates are orthogonal to each other, a backlight is applied from the side of one polarizing plate, and the luminance Y2 of the light passing through the other polarizing plate is measured. The contrast is calculated by Y1 / Y2 using the obtained measurement value. Here, Nitto Denko G1220DUN was used as the polarizing plate, and a color luminance meter BM-5 (manufactured by Topcon Corporation) was used as the measuring instrument.

  When a film is formed by applying the colored curable resin composition of the present invention on a substrate, the dry thickness of the film is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm. Most preferably, the thickness is 1.0 to 2.5 μm.

As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, solid-state imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicone substrate and a plastic substrate. On these substrates, usually, black stripes for isolating each pixel are formed.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

  As the application of the colored curable resin composition of the present invention, the application mainly to the pixel of the color filter has been mainly described, but it goes without saying that the application can also be applied to the black matrix provided between the pixels of the color filter. As for the black matrix, except that a black colorant such as carbon black or titanium black is added to the composition for forming a colored pattern of the present invention as a colorant, pattern exposure, It can be formed by alkali development and then post-baking to accelerate the curing of the film.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises the color filter of the present invention.
More specifically, an alignment film is formed on the inner surface side of the color filter, is opposed to the electrode substrate, and the gap is filled with liquid crystal and sealed to obtain a panel which is the liquid crystal display element of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

Example 1
Components having the following composition were mixed to prepare a pigment dispersion.
[Contains pigment dispersion]
(A) Pigment C.I. I. Pigment Red 254 5 parts C.I. I. Pigment Red 177 5 parts, dispersion resin BYK-161 (active ingredient 30% by weight) manufactured by Big Chemie 13.3 parts, (b) solvent 32.7 parts of propylene glycol monomethyl ether acetate A clear resist was prepared.
[Clear resist formulation]
(C) Binder resin Acrylic resin having a repeating unit represented by the following formula (B) 4.0 parts (c) Polymerizable monomer Dipentaerythritol hexaacrylate 4.0 parts (d) Photopolymerization initiator
2- (2-Chlorophenyl) -4,5-diphenylimidazole dimer
0.4 parts
4,4'-bis (diethylamino) benzophenone 0.2 part 2-methylbenzothiazole 0.4 part (e) polymer surfactant (polymer surfactant described in Table 1) 0.04 part ( b) Solvent 50 parts of propylene glycol monomethyl ether acetate

The pigment dispersion and the clear resist were mixed and stirred and homogenized, 300 g of zirconia beads having a particle diameter of 0.5 mm were added, and the mixture was dispersed by shaking for 5 hours with a paint conditioner. Then, it filtered and the uniform colored curable resin composition was obtained.
The following evaluation was performed about the obtained colored curable resin composition.

(Coating defects)
The obtained colored curable resin composition was applied onto a 550 mm × 650 mm glass substrate (1737, manufactured by Corning) at a coating speed of 200 mm / sec using a slit coater (head coater, head mounted by Faster). Carried out. Thereafter, it was dried in an oven at 90 ° C. for 60 seconds (pre-baking). The film thickness of the dry film was 1.2 μm.
Application of 200 sheets was performed under the above conditions (application interval 20 seconds), and the surface of the 200th application surface was observed with an optical microscope.
The evaluation index is as follows, and Δ is the lower limit of the practical allowable range. The results are shown in Table 1.
○: The number of defects is less than 1 per 0.25 square meters Δ: The number of defects is 1 or more per 0.25 square meters and less than 5 ×: The number of defects is 5 or more per 0.25 square meters thing

(Thickness unevenness)
The obtained colored curable resin composition is discharged from a discharge port of a slit die 12 having a width of 550 mm in which a protruding shim 10 as shown in FIG. 1 is incorporated as shown in FIG. It applied to the glass substrate 14 (Corning Corp. 1737, 0.7-mm thickness) so that a gap might be set to 2.0 micrometers after a post-baking process with a gap of 100 micrometers. In addition, the dimensional unit in FIG. 1 is mm.

At this time, the fluctuation of the streaky film thickness unevenness 18 caused by the protrusions of the shim 10 was measured with a stylus type film thickness meter DECTAC-3 manufactured by ULVAC after post-baking.
The evaluation index is as follows. The results are shown in Table 1.
○: Thickness unevenness within ± 1% Δ: Thickness unevenness exceeds ± 1% and within ± 2% ×: Thickness unevenness exceeds ± 2%

(contrast)
Application was performed at a coating speed of 200 mm / sec on a 550 mm × 650 mm glass substrate (1737, manufactured by Corning) using a slit coater (head coater, head mounted by Faster). Thereafter, it was dried in an oven at 90 ° C. for 60 seconds (pre-baking). The film thickness of the dry film was 1.2 μm.
The entire surface of the coating film is exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film is exposed to a 1% aqueous solution of an alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). Covered and rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. The film exposed and developed as described above is heat-treated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored resin film (colored pattern) for the color filter on the glass substrate. A filter substrate (color filter) was produced.
A polarizing plate is placed on the colored resin film (colored pattern) of the colored filter substrate, the colored resin film is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when orthogonal are measured using BM-5 manufactured by Topcon Corporation. did.
A value obtained by dividing the parallel brightness by the orthogonal brightness (= the brightness when parallel / the brightness when orthogonal) was used as an index for contrast evaluation. The results are shown in Table 1.

(Examples 2 to 11)
A colored pattern was formed and evaluated in the same manner except that the specific surfactant (e) used in Example 1 was changed to the compounds shown in Table 1. The results are shown in Table 1.

(Comparative Examples 1-2)
A colored pattern was formed and evaluated in the same manner except that the specific surfactant (e) used in Example 1 was changed to the compounds shown in Table 1. The results are shown in Table 1.

(P-1): MEGAFAC F-178K manufactured by Dainippon Ink & Chemicals, Inc.
(P-2): MEGAFAC F-470 manufactured by Dainippon Ink & Chemicals, Inc.
(P-3): Dainippon Ink & Chemicals, Inc. MEGAFAC F-473
(P-4): Dainippon Ink & Chemicals, Inc. MEGAFAC F-475
(P-5): MEGAFAC F-476 manufactured by Dainippon Ink & Chemicals, Inc.
(P-6): Dainippon Ink & Chemicals, Inc. MEGAFAC F-472
(P-7): Specific surfactant produced by the production method of (P-7), weight average molecular weight 40,000 (P-8): produced by the production method of (P-8) Specific surfactant, weight average molecular weight 20,000 (P-9): Specific surfactant produced by the production method of (P-9), weight average molecular weight 50,000 (P-10): (P- 10) The specific surfactant produced by the production method of 10), weight average molecular weight 80,000 (P-11): The specific surfactant produced by the production method of (P-11), weight average molecular weight 10,000 (Q-1): MEGAFAC F-177 manufactured by Dainippon Ink & Chemicals, Inc.
(Q-2): Sumitomo 3M FC430

  As is clear from the results in Table 1, the colored curable compositions of Examples 1 to 11 have few defects when slit coater coating is performed using the colored curable composition, and the film thickness unevenness is small. Can be obtained. Furthermore, a high-contrast coloring pattern can be obtained.

It is a top view which shows the shim used for application | coating of a color resist in an Example. It is a perspective view which shows the application state by the slit die which attached the shim of FIG.

Explanation of symbols

10 Shim 12 Slit die 14 Glass substrate 16 Color resist 18 Streaks

Claims (9)

(A) a coloring material, (b) a solvent, (c) at least one selected from the group consisting of a polymerizable monomer and a binder resin, (d) a photopolymerization initiator, and (e) a fluoroaliphatic group as a side chain. A colored curable resin composition comprising a polymer surfactant having the same. (E) The fluoroaliphatic group in the polymer surfactant having a fluoroaliphatic group in the side chain is derived from a fluoroaliphatic compound produced by a telomerization method or an oligomerization method. The colored curable resin composition according to claim 1. 3. The fluoroaliphatic group in the polymer surfactant (e) having a fluoroaliphatic group in the side chain is a group represented by the following general formula (I): The colored curable resin composition described in 1.

(In Formula I, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents a single bond or a divalent linking group, and m represents an integer of 0 or more. , N represents an integer of 1 or more.) The coloring pattern formation method characterized by including the process of apply | coating the colored curable resin composition of any one of Claims 1-3 by the slit coat method. A colored pattern formed by the colored pattern forming method according to claim 4. The manufacturing method of a color filter characterized by including the process of forming a colored pattern by apply | coating the colored curable resin composition of any one of Claims 1-3 by the slit coat method. A color filter manufactured by the manufacturing method according to claim 6. The color filter according to claim 7, wherein the contrast is 5000 or more. A liquid crystal display element using the color filter according to claim 8.

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