TW201035049A - Colored photopolymerizable composition, method for producing colored pattern, and color filter and liquid crystal display device with the color filter - Google Patents

Abstract

A colored photopolymerizable composition, containing a compound (A) represented by the following formula (1), polymerizable compound (B) and a coloring agent. In the formula (1), Y.sup.1, Y.sup.2 and Y.sup.3 are respectively independent and represent hydrogen atoms or alkyl groups of 1 to 4 carbon atoms, wherein at least two of Y.sup.1, Y.sup.2 and Y.sup.3 are methyl groups. R.sup.1 is an alkyl group of 1 to 6 carbon atoms. R.sup.2 represents a hydrogen atom or an alkyl group of 1 to 6 carbon atoms. X represents a monovalent substituent. n is an integer of 0 to 5.

Description

[Technical Field] The present invention relates to a coloring photopolymerizable composition, a method of forming a colored pattern, a color filter, and a liquid crystal display device. [Prior Art] The colored photopolymerizable composition is, for example, a photopolymerization initiator added to a polymerizable compound having an ethylenically unsaturated bond. Since the photopolymerizable composition is polymerized and cured by irradiation with light, it is applied to a photocurable ink, a photosensitive printing plate, a color calender sheet, various resistors, and the like. Further, as the colored photopolymerizable composition, for example, other forms in which acid is generated by irradiation of light and the generated acid is used as a catalyst are also known. Specifically, it is applied to: a material for image formation, anti-counterfeiting, and energy line quantity detection by a color reaction of a dye precursor using a generated acid as a catalyst; and a decomposition reaction using the generated acid as a catalyst It is used for semi-conducting 襄 1^ TFT (Thm Fllm Transistor) manufacturing, color filter manufacturing, micro-mechanical parts manufacturing and other positive resists. In recent years, the color-polymerizable composition which is sensitive to light sources of short-wavelength (365 nm or 405 nm), and the compound which exhibits excellent sensitivity to the light source of the above-mentioned neon wavelength, For example, the requirements for photopolymerization initiators are increased. However, generally, a photopolymerization initiator excellent in sensitivity lacks stability, and therefore a photopolymerization initiator which satisfies the stability over time while improving the sensitivity is desired. Therefore, 'photopolymerization as a coloring photopolymerizable composition is used for the initiation of photopolymerization 143900.doc 201035049, in the specification of U.S. Patent No. 4,255,513, U.S. Patent No. 4,459,145, issued on the Japanese Patent Laid-Open No. An oxime ester derivative is proposed in Japanese Laid-Open Patent Publication No. 2001-233842. However, these known oxime ester derivatives have low absorbance at a wavelength of 365 nm and a wavelength of 4 〇 5 nm, and thus cannot be satisfied from the viewpoint of sensitivity. In addition, as a coloring photopolymerizable composition, it is also desired to have excellent sensitivity over time and excellent sensitivity to light of short wavelengths such as 365 nm and 4G5 nm. Further, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2-195425 discloses a coloring radiation-sensitive composition for a color filter containing a ruthenium compound, but with respect to stability over time and sensitivity to light of a short wavelength. In the coloring photopolymerizable composition for a color filter, the reproducibility of the color tone after the pattern y is a new subject, and it is strongly desired to improve the problem that the coloring property changes with time. In addition, in order to enlarge the color reproduction area, it is strongly required to display the color of the liquid crystal display; the light # becomes a coloring density of the color of the color. If a large amount of coloring agent is added to achieve the same S color/agricultural degree, the photosensitive material may be caused. The degree is insufficient, and the tendency of pattern defects frequently occurs on the body. Furthermore, in order to eliminate this deficiency, it is necessary to irradiate light of higher energy, so that the exposure time is prolonged, and the manufacturing is good: the monthly decrease is marked. In view of the above, the color filter is colored by the color filter, and the mouthpiece is desirably contained in a high concentration, and has good pattern formability. On the other hand, in order to improve the productivity of the exposure step and the development step, it is proposed to form a pattern by exposure using field light (refer to Japanese Laid-Open Patent Publication No. 143900.doc No. 201035049-287614). The laser lamp used by the laser ji Μ 丄 J μ J π 逋 , , 其 其 其 其 其 其 其 车 车 车 车 车 车 车 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水The features of the cover are highly anticipated. However, the use of the above-mentioned prior art is also due to the lack of visibility, one-I:= the characteristics of the requirements. In addition, the total power of the color (four) is reduced as an exposure. Do not use larger masks

Ο Japanese Patent Laid-Open No. 2__767. No. 9 and Japanese Patent No. 8-8:1866. However, specific materials have not been disclosed, and it is desirable to provide a material that is highly sensitive to such devices. 'The Summary of the Invention' [Problems to be Solved by the Invention] A first object of the present invention is to provide a pattern in which a straight line of a pattern can be obtained without defects, and a color having a wide development latitude and excellent developability can be formed. A patterned colored photopolymerizable composition. A second object of the present invention is to provide a method for forming a colored pattern having excellent pattern formation property, wide development latitude, and excellent productivity. Further, a third object of the present invention is to provide a pattern having good shape and excellent productivity. A color filter and a liquid crystal display device including the color filter. [Means for Solving the Problem] The inventors of the present invention have repeatedly conducted intensive studies and solved the above problems by using a ruthenium compound of a specific structure. The specific method for solving the problem of class 143900.doc 201035049 is disclosed below. < 1 > A colored photopolymerizable composition comprising (A) a compound represented by the following formula (丨), (B) a polymerizable compound, and (〇 coloring agent: [Chemical Formula 1]

' , gossip &lt; king 7 固马 1f storm; K / is a slave number 1 ~ 6 alkyl, R2 represents a hydrogen atom, or a carbon number 丨 ~ 6 alkyl · X represents a monovalent substituent, η is 〇 An integer of ~5. &lt;2&gt; The color photopolymerizable composition of (1), wherein the content of the compound represented by the formula (i) (1) is relative to the total solid content of the colored photopolymerizable composition. It is 0.1% by mass to 3% by mass. &lt;3&gt; The color photopolymerizable composition of <1> or <2> wherein the content of the (β) polymerizable compound is 5% by mass to 80% based on the total solid content in the colored photopolymerizable composition. quality%. The colored photopolymerizable composition according to any one of the above-mentioned items, wherein the content of the coloring agent (C) is 10% by mass based on the total solid content of the coloring photopolymerizable composition. ~7〇% by mass. <5> The color photopolymerizable composition of any one of <1> to <4>, wherein the (C) colorant is a pigment, and further contains (9) a pigment dispersant 〆6 such as a color light of 5. The polymerizable composition wherein the content of the above (9) pigment dispersion 143900.doc 201035049* is from 40% by mass to 40% by mass based on the total solid content in the colored photopolymerizable composition. And a method of forming a colored pattern, comprising: forming a colored photopolymerizable composition layer by using the colored photopolymerizable composition according to any one of 1 to &lt;6&gt;; a step of exposing the layer of the colored photopolymerizable composition to a pattern and hardening it; and 0 a step of removing a portion of the uncured colored photopolymerizable composition. &lt;8&gt; A color filter which has a colored pattern formed by using a method such as &lt;7&gt; on a support. &lt;9&gt; A liquid crystal display device comprising a color filter of &lt;8&gt;. [Effects of the Invention] According to the present invention, it is possible to provide a colored photopolymerizable composition which is excellent in linearity and non-defective pattern, and which can form a coloring pattern having a wide development latitude and excellent developability, and can provide a colored photopolymerizable composition. A method for forming a color pattern having excellent pattern formation property, wide development latitude, and excellent productivity, and further, a color filter having a good pattern shape and excellent productivity, and a color filter having the color filter can be provided. Liquid crystal display device. [Embodiment] Hereinafter, a colored photopolymerizable composition of the present invention, a method for forming a colored pattern using the colored photopolymerizable composition, a color filter having the colored pattern, and a color filter using the color filter are used. The liquid crystal display device of the film will be described in detail. The colored photopolymerizable composition of the present invention contains: (A) a compound represented by the formula (i) of 143900.doc 201035049 (hereinafter, sometimes referred to as a specific anthracene compound (B) polymerizable compound, and ( 〇 Coloring agent Q. First, the coloring photopolymerizable composition of the present invention will be described. <Compound represented by the general formula (1)&gt; The colored photopolymerizable composition of the present invention contains the following general formula (i) the compound represented (specific oxime compound).

(1) or an alkyl group of carbon number. Among them, at least one of γ1, γ2, and γ3 is a methyl group. ... is a burning group of carbon number 6, and r2 represents a hydrogen atom or a burning group having a carbon number of 66. χ represents that the monovalent substituent 'η is an integer of 〇~5. The specific ruthenium compound of the present invention represented by the above formula (1) is one having a maximum absorption wavelength in the range of 35 Å to 48 Å in the wavelength region of 3 〇〇 nm or more. The compound has an absorption compared to the cut-off compound in the long wavelength region. Therefore, when exposed to a light source of 355 nm or 365 nm or 405 nm, excellent sensitivity is exhibited. From the viewpoint of sensitivity, the specific erbium compound of the present invention has a molar absorption coefficient at 365 nm of 2 〇, 〇〇〇 〜 2 〇〇 000 000 ' ' ' ' ' ' ' ' ' The absorbance coefficient was measured by using an ultraviolet-visible spectrophotometer (Carry 5 spectr 〇ph〇t〇meter manufactured by Vadan Co., Ltd.), J43900.doc 201035049, using an ethyl acetate solvent at a concentration of 〇_〇1 g/L. The specific ruthenium compound of the present invention has a function as a photopolymerization initiator which is decomposed by light to accelerate the polymerization of (B) a polymerizable compound. In particular, a specific ruthenium compound has excellent sensitivity to a light source of 365 nn^l4〇5 nm, and thus, when used as a photopolymerization initiator, in combination with a polymerizable compound in a coloring photopolymerizable composition Play excellent results. The colored photopolymerizable composition of the present invention can form a cured film having high sensitivity to light having a wavelength of 365 nm or 405 nm, excellent stability over time, and further suppressing coloration caused by heating. Although the detailed mechanism is not known, the specific increase in the amount of radicals generated by the specific ruthenium compound has a structure that absorbs light and suppresses radical re-bonding at the time of cracking, thereby achieving high sensitivity. Further, it is considered that the reason for suppressing the radical rebonding is to suppress the reaction of the decomposition products of the specific ruthenium compound with each other during heating, and to suppress the coloration derived from the reaction. Further, in the present invention, the coloring caused by the heating of the cured film is evaluated, and the color difference AE*ab is used. Here, the color difference AE*ab can be measured by using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. As a condition for evaluation, first, the color photopolymerizable group of the present invention is used in an ultrahigh pressure mercury lamp proximity exposure machine or a xenon ray stepwise exposure apparatus (365 nm) at 1 〇mj/cm2 to 2,500 mJ. Exposure is performed in various exposures in the range of /cm2 to form a cured film. Further, the cured film was heated at 200 C for 1 hour after development as necessary. By using / to determine the color difference AE*ab before and after heating of the cured film, the coloring state caused by the heating of the film 143900.doc 201035049 can be evaluated. When the colored photopolymerizable composition of the present invention is used, the color difference AE ab before and after heating can be made 3 or less, and the color change due to heating can be greatly reduced, and a color filter having high color purity can be obtained. The specific fat compound of the present invention can be synthesized by the method shown in, for example, Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. Y1, Y2 and Y3 in the formula (1) each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least two of Y1, Y2 and Y3 are a mercapto group. Further, R1 is an alkyl group having 1 to 6 carbon atoms, and r2 represents a hydrogen atom or an alkyl group having a carbon number of 6. Here, the alkyl group which is a carbon number of Ri and R2 is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a tert-butyl group, a pentyl group, an isopentyl group, The neopentyl group, the third amyl group, the hexyl group, the isohexyl group and the like are preferably a methyl group, an ethyl group and a butyl group. Particularly preferably, when R1 is a methyl group or an ethyl group, r2 is a compound of ethyl*butyl group. X in the formula (1) represents a valence substituent, preferably a hydrogen atom or a methyl group. η is an integer of 〇~5, preferably 1 or 2. As a preferable structure of a specific hybrid, the following compounds are mentioned. [Chemical 3]

Compound 1 143900.doc 201035049 Ο

Compound 6 The specific two compounds in the color photopolymerizable composition of the present invention are in the total solid content of the coloring photopolymerizable composition (U~30 quality denier is preferably 1 to 25% by mass, particularly preferably 2~) 20% by mass. 〇 〇 口 单 单 单 , 单 单 单 单 单 单 单 单 单 单 单 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 - 201035049 In the range of the effects of the above, a photopolymerization initiator other than the above-mentioned specific compound is used in combination. A known photopolymerization initiator which can be used in combination is a compound which initiates polymerization of the following polymerizable compound by decomposition of light. a preferred foot: an area of 300 nm has an absorber. Specifically, for example, a functional compound, a singular compound, a singular compound, a condensed character, a benzoin compound, an organic peroxidic compound, Azo compound,: a soy compound, a #nitro compound, a metallocene compound, a bis-salt compound, an organic lysine compound, a dibasic acid compound, a (four) compound, a stray salt compound, a mercaptophosphine (oxide) compound. Specifically, the polymerization initiator disclosed in paragraphs [0081] to [0139] of the above-mentioned Japanese Patent Laid-Open Publication No. Hei 6-78749, and the like. (B) Polymerizable compound &gt; Colored photopolymerizability The (B) polymerizable compound which can be used in the composition is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and may have at least one, preferably two or more terminal ethylenically unsaturated groups. The above-mentioned compound group is widely known in the industrial field, and it can be used without particular limitation in the present invention. These have, for example, a monomer, a prepolymer, that is, a dimer, and a trimer. And chemical forms of the oligomers or mixtures thereof, and copolymers thereof, etc. Examples of the monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, Butenoic acid, methacrylic acid, maleic acid, etc.) or esters thereof, guanamines, preferably vinegar, unsaturated acid and aliphatic polyamine using unsaturated carboxylic acid and aliphatic polyol compound Indoleamines of the compound, again, 143900.d Oc 12 201035049 It is also preferred to use an addition reaction of an unsaturated carboxylic acid ester or a guanamine containing a nucleophilic substituent such as a hydroxyl group or an amine group or a fluorenyl group with a monofunctional or polyfunctional isocyanate or epoxy compound. And a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid, etc. Further, an unsaturated carboxylic acid ester or guanamine containing an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol Addition reactants of the class, amines, and mercaptans are also preferred, and further contain an unsaturated acid ester or a chiral amine and a monoterpene group or a derivatizing substituent such as a self-priming group or a phenyloxy group. Substituted reactants of polyfunctional alcohols, amines, and mercaptans are also preferred. Further, as another example, the unsaturated carboxylic acid may be replaced by an unsaturated phosphonic acid, styrene, acethanide or the like. a group of compounds. Examples of the polymerizable compound include monofunctional ones such as polyethylene glycol mono(indenyl) acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl(mercapto)propionate. Acrylate or mercapto acrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tris(meth)acrylic acid s曰, neopentyl glycol di(meth)acrylate, pentaerythritol three ( Methyl)propene O is pentylenetetraol tetra(meth)acrylic acid vinegar, dipentaerythritol hexa(methyl) acrylate vinegar, hexanediol (meth) acrylate vinegar, trimethylolpropane tris(propylene oxypropyl) Ether, tris(acryloxyethyl)isocyanurate, (meth)acrylate after addition of epoxy bromide or propylene oxide to polyfunctional alcohol such as glycerol or dimethylacetone A poly(ro) propionate obtained by a compound, pentaerythritol or dipentaerythritol. Further, it is also preferable to use a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a trans group. Specific examples thereof include those disclosed in Japanese Patent Publication No. Sho 48-41 708. It is disclosed in i molecule 143900.doc 13 201035049 A polyisocyanate compound containing two or more isocyanate groups is added to one molecule of a hydroxyl group-containing ethylene monomer represented by the following formula (A). More than one polymerizable vinyl vinyl urethane compound or the like. CH2-C(R)CO〇CH2CH(R5)〇h (A) (wherein, in the formula (A), R4 and R5 represent H or CH3, respectively). In addition, as described in Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 2_32293, Japanese Patent Publication No. 2_16765, the urethane-based bismuth citrate or Japanese Patent Special Publication No. Sho 58_4986G, Japanese Patent Special Public Show Amino formate compound having an epoxy ethylene skeleton as disclosed in Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 is also preferred. Further, the molecule having an amine structure or a sulfide structure is disclosed in the molecule disclosed in Japanese Patent Application Laid-Open No. Sho 63- 2776 S3, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. By adding a polymerizable compound, a color photopolymerizable composition having a very excellent photospeed can be obtained. Examples of the other examples include polyester acrylates and ring-openings disclosed in Japanese Patent Laid-Open Publication No. SHO-48-64183, Japanese Patent Publication No. Sho 49-43191, Japanese Patent Publication No. Sho. The epoxy acrylate s, which is obtained by reacting an oxy resin with (meth) acrylic acid, is a polyfunctional acetoacetate or methacrylic acid vinegar. X, and a specific unsaturated compound disclosed in Japanese Patent Publication No. Sho. No. 6, No. 6, Japanese Patent Publication No. Hei. No. Hei. An acid compound or the like. Further, the structure containing a perfluoroalkyl group disclosed in Japanese Laid-Open Patent Publication No. Sho 61-22048 can be used in a manner similar to 143900.doc -14-201035049. Furthermore, it can also be used in the 曰 黏 adhesion association 诸 〇 〇 ..

No. 7, 300 to 308 (1984) are introduced as photocurable monomers and oligomers. ❹ ❹ The details of the method of using the structure of the compound such as β, whether it is used alone or in combination, can be arbitrarily set in accordance with the performance design of the final photosensitive material. For example, it is selected in accordance with the viewpoint as described below. In terms of the speed of light, it is preferred that the structure has a large content of unsaturated groups per molecule, and in many cases, it is preferably two or more. Further, in order to increase the strength of the image portion, that is, the cured film, it is preferably a trifunctional or higher functional group, and a different functional group or a different polymerizable group (for example, acrylic vinegar or methyl acrylate vinegar) is used in combination. A method of adjusting both photosensitivity and strength is also effective in the case of a styrene-based compound or a vinyl bond-based compound. From the viewpoint of the development speed or the precipitation in the developer, a compound having a molecular weight or a hydrophobicity in a preferable range can be selected. Moreover, for the compatibility and dispersibility of other components in the photosensitive layer (for example, 'adhesive polymer, initiator, colorant 箄, 士士巴巴), the selection and use of the poly compound are also As an important factor. From these viewpoints, the content of the polymerizable compound is preferably from 5:25 to 75% by mass based on the total solid content of the composition of the composition. A good ruler ’ again::: The polymerizable compound may be used alone or in combination. In addition, regarding the size of inhibition of oxygen polymerization, resolution, refractive index change, surface adhesion, etc., 143900.doc 201035049

In other words, the method of using the polymerizable compound can be arbitrarily selected and used in an appropriate amount. &lt;(c) Colorant&gt; The colored photopolymerizable composition of the present invention contains (C) a colored sword, a color photopolymerizable sigma which can obtain a desired color by containing a coloring agent'. Further, since the color photopolymerizable composition of the present invention contains an excellent ninth degree (A) bismuth compound as a light source of a short skin length of 3 15 nm or 400 nm, even if it is high When the concentration contains a coloring agent, it can be hardened by sensitivity. 'square

For the coloring agent used in the color photopolymerizable composition, it is not particularly preferable to use one of the previously known various dyes or pigments, or to use two kinds of the same coloring photopolymerizable composition. Use and choose. When the color photopolymerizable composition of the present invention is applied to the production of a color light sheet, the color forming the color filter may be used: (4), red), G-green, -, blue, etc. Li D M II:: Any of the black colorants commonly used in the formation of I:

Color crossing light "Tour coloring agent into the "::: coloring agent" enumeration is suitable for I: coloring material, can use the previously known various inorganic pigments, preferably high transmission machine (four) or organic pigment, if considering The metallization I: 'is exemplified by metal oxides, metal-missing salts, etc.; steel, chin, heart, specifically, metal oxides, metal oxides of the materials, and the above metals 4 143900.doc - 16- 201035049 Combined oxide. The pigment which can be preferably used in the present invention is exemplified below. The present invention is not limited to these. C.I. (colour index, pigment index) pigment yellow u, 24, 1 〇 8 1 〇 9, 11 〇, 138, 139, 150, 151, 154, 167, 18 〇, 185 c. l · pigment orange 36, 71;

CI, Pigment Red 122, 150, 171, 175, 177, 2 () 9, 224 242, 254, 255, 264; CI Pigment Green 7, 36, 37, 58; C·1·Pigment Violet 19, 23, 32 CI Pigment Blue 15 ·· 1,15 : 3,15 : 6,16,22,6〇79 , 80 ; C-Ι.Pigment Black 1 These organic pigments can be used alone or in order to improve the color purity. Various organic pigments are used in combination. Specific examples of the above combinations are shown below. For example, 'as a red pigment, you can use the onion-based m-based pigment alone, and the material is mixed: (4) pigment, or at least one kind of dip-type and disazo-based yellow pigment, iso-porphyrin-based yellow v. A mixture of an anthrone-based yellow pigment or a quinone-based red pigment. f, 乂 如 如 ' ' 作为 作为 作为 作为 作为 作为 作为 CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI CI For example, CI Pigment Red 254 is exemplified as the ketone pigment of D, and it is preferably mixed with CI Pigment Yellow 139 in terms of color reproducibility. From the point of view of the color purity of the fish and the color deviation, the mass ratio of the page pigment to the red pigment (PQ (vapor pigment/red pigment) is better 143900.doc •17· 201035049 is 5/100 ～50/100. Especially as the above mass ratio, the best range is from 10/100 to 30/100. Furthermore, when the red pigments are combined with each other, the chromaticity can be adjusted. For the pigment, the phthalocyanine pigment can be used alone, or the bismuth phthalocyanine pigment and the bisazo yellow pigment, the quinacridone yellow pigment, the fluorenyl azo yellow pigment or the hexamethine pigment can be used. This is a yellow pigment. For example, as the above examples, it is preferred that 匕 〗 〖 Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CJ. Pigment Yellow 138, CJ Pigment Yellow 139, ci Pigment Yellow 150, c丄Pigment Yellow 18〇 or cj Pigment Astragalus 85. In terms of color purity and hue deviation, the negative ratio of yellow pigment to green pigment (yellow pigment/green pigment) is preferably 5/1 〇〇~15〇/1〇〇 range. Also, if it exceeds 150/100, there is a dominant wavelength The near-long wavelength is different from the target hue of the NTSC (Nati〇nal Television System Committee). As the above-mentioned texture ratio, it is particularly good in the range of 30/100 to 120/100. As the blue pigment, a phthalocyanine pigment may be used alone, or a mixture of a phthalocyanine pigment and a ruthenium-based purple pigment may be used. For example, a preferred ◎ is a ci pigment blue 15 ··6 and (: The mixture of bismuth pigment violet 23. The mass ratio of purple pigment to blue pigment (purple pigment/blue pigment) is preferably in the range of 0/100 to 60/100, more preferably 4 Å/1 Torr or less. In the case of using a colored photopolymerizable composition when forming a black film such as a black matrix, black (black colorant) is used as a colorant. In the present invention, various known blacks can be used as the black colorant. Pigments or black dyes, especially in the case of a small amount of high optical density, 143900.doc -18- 201035049 points, preferably carbon black, black, titanium oxide, iron oxide, oxidized, graphite, etc. Among them, It is preferable to include at least one of carbon black and black. The black colorants may be used singly or in combination of two or more. The volume resistance of carbon black is measured as follows. , a carbon black and a methacrylate vinegar and methacrylic acid in a molar ratio of 7 〇: 3 〇 a copolymer of 0 (mass average molecular weight of 30, _) mass ratio of 20: 80, The coating liquid was prepared by dispersing black into propylene glycol monoterpene, and coated on a chromium substrate having a thickness of 1.1 mm and 10 cmxi〇cm 2 to prepare a coating film having a dry film thickness of 3 μη!, and further in a heating plate, at 22 Hey. 〇 After the coating film was heat-treated for about 5 minutes, the volume was measured in an environment of 23 t and a relative humidity of 65% by using a surface resistivity meter manufactured by Mitsubishi Chemical Co., Ltd. according to JIS κ. resistance. Further, it is preferred that the volume resistance value is ΙΟ5 Ω·cm or more, more preferably Ο is more than i 〇 6 & cm, and particularly preferably carbon black of I07 n.cm or more. Further, as the carbon black, for example, it is also possible to use the Japanese Patent Laid-Open Patent Publication No. 0988, the Japanese Patent Application Laid-Open Publication No. U0989, the Japanese Patent Laid-Open Publication No. Hei 10-330643, and the Japanese Patent Special Publication No. Patent Publication No. Hei. Further, as the titanium black to be used in the present invention, for example, 12S, 13M, 13M-C, 13R-N manufactured by Mitsubishi Chemical Corporation, and Tilack D manufactured by Akasaka Chemicals Co., Ltd. 143900.doc 19 201035049 Ltd. A coloring agent which can be used in the coloring photopolymerizable composition is preferably a pigment having an average particle diameter r (unit: nm) of 20 $300, preferably 25 $250, particularly preferably 30 Sr S200. By using the above average particle diameter α pigment', red and green pixels having high contrast and high light transmittance can be obtained. The "average particle diameter" as used herein means the average particle diameter of the secondary particles in which the primary particles (single crystallites) of the pigment are aggregated. Further, the particle size distribution of the secondary particles of the pigment which can be used in the present invention (hereinafter, simply referred to as "particle size distribution") is preferably (average particle diameter ± 〇〇) secondary particles within 〇 nm It is more than 7 mass% or more of the whole, and it is preferably more than mass%. ~|1 series of pigments can only be obtained by the following methods: 2, the commercially available pigments and other pigments used as appropriate (Ping (4) ^ 300 Cong) are better to be dispersed Agent and solvent = For example, a bead mill, a machine, etc., is pulverized to form a pigment dispersion dichroic: put it: the pigment obtained is preferably pre-formed. The shape of the nighttime light is used for coloring the photopolymerizable composition: from the viewpoint of the coloring agent contained in the photopolymerizable composition and the development latitude, in the case of colored light, the color solid matter is relatively Preferably, it is 1 〇 ~ mouth f, and the total of the compound is further preferably 1 〇 θ, 里 'more preferably 10 to 65 mass %, 疋 〇 6 〇 mass 〇 / 〇. &lt;(D) Pigment Dispersant&gt; In the case where the colored photopolymerizable composition contains a pigment (in the case of a colored sword, 143900.doc • 20-201035049, it is preferable to add the genus (D) Pigment Dispersant from the viewpoint of dispersibility. VIII: (D) Pigment/Knife Agent's can be used in the coloring photopolymerizable composition of the present month. Indoleamine and pots, «acids and their salts, high molecular weight unsaturated acid vinegar, modified polyamines; acid oxime modified J · biopolymerized S 曰, modified poly (methyl) acrylate vinegar, Methyl)acrylic acid

Copolymer, naphthalenesulfonaldehyde condensate], and polyoxyethylene alkyl phosphate: polyoxyethylene alkylamine, amine, pigment derivative, and the like. The polymer dispersant can be classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure. The knives of the knives are adsorbed on the surface of the pigment to prevent re-aggregation. Because of the better structure, the terminal-modified polymer having a fixed portion to the surface of the pigment, graft type Polymer, block type of molecule. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the surface of the pigment. Specific examples of the pigment dispersant which can be used in the color photopolymerizable composition of the present invention include "Disperbyk-101 (polyammoniumamine phosphate) manufactured by BYK Chemie Co., Ltd., and 1 〇 7. ), 110 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight is not Saturated polycarboxylic acid), EFKA 4047, 4050, 4010, 4165 (polyamine phthalate) EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high 143900.doc -21 - 201035049 molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (anthocyanine derivative), 6750 (azo pigment derivative), "Ajisper PB821, PB822" manufactured by Ajinomoto Fine-Techno Co., Ltd., "Flowlen TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300 (acrylic) manufactured by Kyoritsu Chemical Co., Ltd. Copolymer)", "Disparlon KS-860, 873SN, 874, # 2150" manufactured by Nanben Chemical Company酉曼), #7004 (Polyether), DA-703-50, DA-705, DA-725", "Demol RN, N (naphthalene sulfonic acid furfural polycondensate), MS, C manufactured by Kao Corporation , SN-B (aromatic sulfonic acid formaldehyde polycondensate), "Homogenol L-18 (polymer polycarboxylic acid)", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamin 86", "Solsperse 5000", 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 manufactured by Lubrizol (a polymer having a functional portion at the distal end), 24000, 28000, 32000, 38500 (grafted polymer), and "Nikkol T106 (polyoxyethylene sorbitan monooleate) manufactured by Nikko Chemical Co., Ltd., MYS-ΙΕΧ (polyoxyethylene monostearate) and the like. These pigment dispersants may be used singly or in combination of two or more. In the present invention, it is particularly preferred to use a pigment derivative in combination with a polymer dispersant. The content of the pigment dispersant in the colored photopolymerizable composition is preferably from 1 to 80% by mass, more preferably from 5 to 70% by mass, even more preferably from 10 to 60% by mass based on the pigment. %. Specifically, in the case of using a polymer dispersant, the amount of the phase used is 143,900.doc -22 to 201035049, and the pigment is preferably in the range of 5 to 100% by mass. Quality - better is the case where the pigment street creature is used, and its usage amount is in the range of 1 to 3 ° ff%, more preferably 3 to 2, with respect to the color quality a:?. in. A circumference, especially good is in the range of 5 to 15 mass 〇 / 。. From the viewpoint of the dispersibility of the pigment of the colorant, the pigment dispersant Ο 8 3 ' is preferably 疋 3% by mass or more for the total solid content in the colored photopolymerizable composition. w Ding - 曰. It is more preferably 5% by mass or more and 35 mass% or less, and further preferably 7% by mass or more and 3% by mass or less. Further, the color photopolymerizable composition may further contain any of the components described in detail below. 'The following' is any component which can be contained in the colored photopolymerizable composition. w &lt; (E) Sensitizer&gt; The colored photopolymerizable composition may contain a sensitizer for the purpose of improving the radical generating efficiency of the radical initiator and increasing the wavelength of the photosensitive wavelength. As the sensitizer which can be used in the present invention, it is preferred to use the electron-moving mechanism or the energy-moving mechanism to sensitize the above (4) compound. The sensitizer which can be used in the present invention is exemplified by those having the following oxime and having an absorption wavelength in a wavelength region of from 300 nm to 45 Å. Preferred examples of the sensitizer include those belonging to the following compounds and having an absorption wavelength in a wavelength region of from 330 to 1 Å to 45 Å. Examples thereof include polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, iridium). , stretching triphenyl, 9,1 〇 二 二 二 、 、 、 、 、 、 、 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Red), sulphurous onion (isopropyl thioxanthene, diethyl thiazolone, chlorthiazepine (4), cyanine (for example, thiocarbonate, anthraquinone), merocyanine (eg, anthocyanins, anthocyanins in carbon), catechins, genus (eg, thioindigo, methylene, blue, toluidine blue), acridines (eg... acridine orange, gas Flavin, acridine flavin, enema (for example, sorghum), squaraine, coumarin (eg, ethylamine scent: 夂 基 基 丑, W class, De, $vinyl benzene, azobis, diphenyl, triphenyl, distyryl, &quot;card: class, porphyrin, spiro compound, quinacridone, Zhi team Benyi, 咕锵 咕锵 compound ... buckymethylene compound, and triple saliva, bismuth compound, G than acid derivative, thiobarbituric acid derivative ketone, benzophenone, thia a heterocyclic compound such as an onion ketone or a ketone ketone, such as an aromatic-B-N-aryl oxazolidinone. The sensitizing agent contains a coloring photosensitive composition from the viewpoint of sensitivity and storage stability. The mass of the total solids, the relatively good summer heat 1, the range of quality, and the better the U0 mass% of the range '~〇 is the range of 2 to 15% by mass. Better &lt; (F) A secondary sensitizer&gt; The colored photopolymerizable composition further contains (1?) a secondary sensitizer which is also preferably used in the present invention, and the auxiliary sensitizer has a further improvement for (A. compound or (E) sensitization The sensitivity of the active radiation of the agent, the effect of inhibiting the polymerization of the (B) polymerizable compound caused by the bamboo bismuth, or the inhibition of hydrazine as an example of the above-mentioned auxiliary sensitizer, and examples thereof include amines.

, for example, M. R 143900.doc .24- 201035049

"Journai 〇fp〇iymer Society" by Sander et al., vol. 3, p. 3 (3) (1972), Japanese Patent Publication No. Sho 44-2〇 189, Japanese Patent Laid-Open No. 51-82102, Japanese Patent Japanese Patent Publication No. Sho 59-138205, Japanese Patent Laid-Open Publication No. SHO-59-138205, Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. Specific examples of the compound disclosed in the publication No. 104, Research Disclosure No. 33825, etc., specifically, triethanolamine, p-dimethylamine ketobenzoic acid ethyl ester, p-nonyldimethylaniline, p-methylthiodimethylaniline Wait. Other examples of the auxiliary sensitizer include mercaptans and sulfides. For example, JP-A-53-702, Japanese Patent Publication No. 55 5〇〇8〇6, and Japanese Patent Laid-Open No. 5_142772 The thiol group disclosed in Japanese Laid-Open Patent Publication No. Hei 56-75643, and the bismuth and the like are exemplified by 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzopyrene Imidazole, 2-mercapto-4(3H)-quinazoline, β-mercaptophthalene, and the like. Further, as another example of the auxiliary sensitizer, an amino acid compound (for example, succinyl glycine acid, etc.), and Japanese Patent Publication No. 48-42965, for example, an organometallic compound (for example, three) A sulfur compound (for example, trithiane, etc.) disclosed in Japanese Patent Publication No. Sho 55-34414, the disclosure of which is incorporated herein by reference. The hardness of the auxiliary sensitizer is preferably 0.1 to 0.1% of the total solid content of the colored photopolymerizable group. The range of 30% by mass, 143900.doc -25- 201035049 is more preferably in the range of 25 mass%, and further preferably Μ, quality. / Range. The oligochromic photopolymerizable composition preferably contains a thiol compound as a secondary sensitizer. The thiol compound may be used singly or in combination of two or more. In the case where a thiol compound is used in combination, only two or more compounds represented by any one of the above formulas may be used in combination, or a compound represented by a different oxime may be used in combination. In the case where the colored photopolymerizable conjugate contains a thiol compound, the curing speed due to the balance between the growth rate of the polymerization of the fluorene and the chain transfer is ruined, and the content thereof is relative to the total solid content of the colored photopolymerizable composition. Preferably, it is preferably in the range of 0.5 to 30% by mass, more preferably in the range of i to ", and more preferably in the range of 3 to 2% by mass. In the colored photopolymerizable composition, a binder polymer is used to improve film properties and the like. As the binder, it is more commonly used. In the case of L organic polymer, it is possible to arbitrarily select water or two: development or weak water development, and it is preferred to select a linear organic a or a linear organic polymer. The A-port system is selected for use not only as skin water, weak water or organic ice...a film tanning agent but also as a water-soluble agent. For example, linear organic polymer = water development is possible. As such a compound, for example, a free radical group having a slow acid group in the Japanese true/side bond is disclosed in Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent No. Sho. Japanese Patent Publication No. Sho 58_12577, and Japanese Patent No. 143900. -26- 201035049 No. 54-25957, Japanese Patent Laid-Open No. 54-92723, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71-48, that is, separate money a monomer or a resin obtained by copolymerizing the same, a monomer containing an acid anhydride alone or a resin obtained by copolymerizing and hydrolyzing or semi-esterifying or semi-aminating the acid anhydride unit, and epoxy resin An epoxy acrylic material modified with an unsaturated monocarboxylic acid and an acid anhydride. Examples of the monomer having a rebel base include acrylic acid, methyl acetoacetic acid, itaconic acid, and butyric acid.

Examples of the monomer containing an acid anhydride include cis-butyl dicarboxylic acid, fumaric acid, and a benzoic acid anhydride. Further, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. Further, it is useful to add a cyclic acid anhydride to a polymer having a hydroxyl group. When an alkali-soluble resin is used as the copolymer, as the copolymerized compound, other monomers than the monomers listed above may be used. Among these, a fluorene (meth)acrylic resin having an allyl group or a vinyl ester group and a carboxyl group in a side chain, and Japanese Patent Laid-Open Publication No. 2000-187322, Japanese Patent Laid-Open No. Hei 2 No. Hei. The alkali-soluble resin having a double bond in a side chain disclosed in the publication, or the film strength, sensitivity, and development of a soluble resin having a guanamine group in a side chain disclosed in Japanese Patent Laid-Open Publication No. 2-242612 The balance of sex is excellent, so it is better. In addition, Japanese Patent Special Fair 7_12〇〇4, Japanese Patent Special Fair 7_12〇〇41, Japanese Special Fair 7-12_2, Japanese Patent Special Fair 8-12424, Japanese Patent Special Open 63_28m4, Japan An acid group-containing urethane-based adhesive disclosed in Japanese Patent Publication No. Sho 63-287947, Japanese Patent No. 4, Kaiping (3) (10), Japanese Patent No. 143900, doc -27-201035049, and JP-A-2002- 10791 The strength of the polymer-based bismuth vinegar-based adhesive polymer having an acid group and a double bond in the side bond disclosed in the polymer ' or the Japanese Patent Laid-Open Publication No. 2002-1 〇 791 8 is excellent in the aspect of low exposure adaptability. More favorable. Further, the film of an acetal-modified polyvinyl alcohol-based adhesive polymer having an acid group disclosed in the European Patent, the European Patent No. 12, 〇〇〇 〇〇〇, and the Japanese Patent Laid-Open Publication No. 2001-3-1866 It is preferable because it has excellent balance of strength and developability. Further, as the water-soluble linear organic polymer, polyvinylpyrrolidone or polyethylene oxide is useful. Further, in order to increase the strength of the hardened film, alcohol-soluble nylon or a polyether of 2,2-bis(4-hydroxyphenyl)-propane and epichlorohydrin is also useful. Among these, especially [benzyl (meth) acrylate / (mercapto) acrylate / other addition polymerizable ethylene monomer] copolymer and [(methyl) propylene diacrylate / (A) The acrylic acid/other addition polymerizable ethylene monomer] copolymer is preferred because it has excellent balance of film strength, sensitivity, and developability. The weight average molecular weight of the binder polymer which can be used in the coloring photopolymerizable composition is preferably 5 or more, and more preferably 10,000 to 300,000. The average molecular weight is preferably the above, and more preferably 2, 〇〇〇 to 250,000. The polydispersity index (weight average molecular weight/number average molecular weight) is preferably UX, and more preferably 1.1 to 10. /etc. Sticky &quot;丨聚聚. The material may be any of a random polymer, a block polymer, a graft polymer, and the like. The binder polymer which can be used in this month can be synthesized by the previously known method 143900.doc -28-201035049. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, and cyclohexanone. These solvents may be used singly or in combination of two or more. * As a binder polymer which can be used for the synthetic color-developing photopolymerizable composition, the radical polymerization initiator to be used may, for example, be a known compound such as an azo initiator or a peroxide initiator. &lt;(H) Polymerization Inhibitor&gt; It is preferable to prevent unnecessary thermal polymerization of (B) a polymerizable compound during production or during storage of the coloring photopolymerizable composition. It is the addition of a small amount of thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor which can be used in the present invention include p-benzoate, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, and benzoquinone. , 4,4,- thiobis(3-methyl-6-tert-butylphenol), 2,2'-sub-T-bis (heart methyl·6_t-butylbenzene), n_ Artesyl phenylhydroxylamine sulfonium salt and the like. The addition amount of the oxime & polymerization inhibitor is preferably from about 0 -01 to about 5 mass% based on the total solid content of the I color photopolymerizable composition. Further, if necessary, in order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as undecanoic acid or behenylamine may be added, and it may be unevenly distributed on the coating film during drying after coating. surface. The amount of the tertiary fatty acid derivative added is preferably from about 5 to about 1% by mass of the total composition. &lt; (I) Adhesion enhancer&gt; In the colored photopolymerizable composition, an adhesion promoter may be added to improve the rigidity of the hard surface such as the support. Examples of the adhesion promoting agent include 143900.doc -29-201035049 decane coupling agent, titanium coupling agent, and the like. As the decane coupling agent, preferred is γ-f-based acryloxypropyltris-oxydecane, γ-methylpropenyloxypropyltriethoxydecane, and propyleneoxypropyltrifoxide. Oxydecane, γ-propylene methoxypropyl triethoxy decane, γ-mercaptopropyl trimethoxy decane, aminopropyl triethoxy oxime phenyl dimethoxy sulphur, best It is γ-methacryloxypropyltrimethoxy oxime. In the total solid content of the colored photopolymerizable composition, the amount of the adhesion promoter is preferably from 0.5 to 30% by mass, more preferably from 7 to 2% by mass. 〇 &lt;(J) Thinner&gt; The colored photopolymerizable composition may also use various organic solvents as a diluent. As the organic solvent used herein, there are mercaptoethyl ketone, cyclohexanyl acetate, ethyl acetate, propylene glycol monoterpene-acetic acid, propylene glycol, monoethyl acetoxyacetate, methoxypropyl acetate, butyrolactone. , methyl lactate, ethyl lactate, and the like. These solvents may be used singly or in combination. The amount of the organic solvent in the colored photopolymerizable composition is preferably such that the concentration of the gj-shaped substance of the colored photopolymerizable composition is from 2 to 60% by mass. &lt; (K) Other Additives&gt; Further, a known additive such as a plasticizer for modifying the physical properties of the hardened film may be added to the colored photopolymerizable composition. As the plasticizer, for example, dioctyl phthalate, di(dodecyl) phthalate, triethylene glycol dioctanoate, diammonium dimercapto diol vinegar, Trimethyl citrate, adipic acid dioctyl, : 143900.doc -30- 201035049 Ethylene glycerol, etc., in the case of using a binder polymer, relative to the total mass of the polymerizable compound and the binder polymer, It can be added in an amount of 1% by mass or less. Further, by containing a fluorine-based organic compound or a surfactant, liquid characteristics (especially fluidity) at the time of producing a coating liquid can be improved, and uniformity of coating thickness or liquid-repellent property can be improved. That is, the interfacial tension between the substrate and the coating liquid is lowered to improve the wettability to the substrate, and the coating property to the substrate is improved. Therefore, even when a film having a reduced number of liquids is formed, a thickness unevenness can be formed. Films of smaller average thickness are more effective in this respect. As the gas-based surfactant, a compound having a fluoroalkyl group or a fluorine-extended alkyl group at any of the terminal, main chain and side chain can be preferably used. The fluorine content of the fluorine-based organic compound is preferably from 3 to 4% by mass, particularly preferably from 7 to 25% by mass. If the fluorine content is effective in the coating thickness uniformity or the liquid-saving property of 2 |&amp;, the solubility in the composition is also good. Further, as the surfactant, various surfactants of nonionic, cationic or anionic surfactants can be used. Preferably, a nonionic surfactant is preferred. As an example of the nonionic surfactant, for example, a polyoxyethylene alkyl group, a polyoxyethylene aryl group (IV), a polyoxyethylene group, a * sugar alcohol group, a monoglycerin, and a monoglycerin are particularly preferable. A nonionic surfactant such as a base. The color-polymerizable composition of the present month makes it possible to increase the strength of the coating film 143900.doc 201035049 and improve the solvent resistance by adding a thermal polymerization component such as an epoxy compound to the thermal polymerization component. The epoxy compound is a compound having two or more epoxy rings in a molecule such as a bisphenol A type, a cresol novolak type, a biphenyl type or an alicyclic epoxy compound. For example, as bisphenol A type, except Epotohto YD-115 'YD-118T ' YD-127 ' YD-128 &gt; YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 Etc. (all manufactured by Dongdu Chemical Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103, etc. (all manufactured by Nagase), Placcel GL-61, GL-62, G101, G102 (all manufactured by Daicel Chemical) Other similar bisphenol F type and bisphenol S type may be mentioned. Further, an epoxy acrylate such as Ebecryl 3 700, 3 701, or 600 (all manufactured by Daicel-UCB) can be used. Examples of the phenolic novolac type include Epotohto YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 (all of which are manufactured by Tohto Kasei Co., Ltd.), and Denacol EM-125 (the above is manufactured by Nagase). As the biphenyl type, 3,5,3',5'-tetradecyl-4,4'-diglycidylbiphenyl, etc. may be mentioned, and as an alicyclic epoxy compound, Celloxide may be mentioned. 2021, 2081, 2083, 2085, Epolead GT-301, GT-302, GT-401, GT-403, EHPE-3 150 (all manufactured by Daicel Chemical), Suntohto ST-3000, ST-4000, ST-50 8 0 , S T-5 1 0 0, etc. (all of which are manufactured by Toho Chemical Co., Ltd.). Further, 1,1,2,2-tetra(p-glycidoxyphenyl)ethane, tris(p-glycidyloxy)methane, triglycidyltris(hydroxyethyl)isocyanate can also be used. Uric acid ester, diglycidyl phthalate, diglycidyl terephthalate, and Epotohto ΥΗ-434, ΥΗ-434L, bisphenol A type epoxy which will be used as the amine type epoxy resin Shrinkage of the resin skeleton modified with dimer acid 143900.doc •32- 201035049 Glycerin S. &lt;Method of Forming Colored Pattern and Color Filter Therewith&gt; Next, a method of forming a colored pattern of the present invention and a color filter having a colored pattern will be described. The color filter of the present invention is characterized in that it has a colored pattern formed by using the colored photopolymerizable composition of the present invention on a support. Hereinafter, a method of forming a colored pattern of the present invention and a color filter having the same will be described in detail. The method for forming a coloring pattern of the present invention is characterized in that the coloring polymerizable composition layer is formed on the support by using the colored photopolymerizable composition of the present invention (hereinafter, simply referred to as "coloring photopolymerization" The step of forming the layer of the colored photopolymerizable composition onto the colored photopolymerizable composition layer and curing it (hereinafter, simply referred to as "exposure step"), and performing development The step of removing the uncured color photopolymerizable composition layer (hereinafter, simply referred to as "development step" as appropriate). Specifically, the colored photopolymerizable composition of the present invention is applied to a support (substrate) directly or via another layer to form a color photopolymerizable composition layer (coloring photopolymerizable composition layer forming step). Exposing into a pattern through a specific mask pattern, and partially curing only the light-irradiated coating film (exposure V-exposure) is developed by using a developing solution (development step), and the steps are repeated to form each color ( A colored pattern of pixels of 3 colors or 4 colors), whereby a color filter can be manufactured. Hereinafter, each step in the method of forming the colored pattern of the present invention will be described. 1439〇〇. (j〇c • 33- 201035049 [Coloring Photopolymerizable Composition Layer Forming Step] In the coloring photopolymerizable composition layer forming step, the colored photopolymerizable composition of the present invention is applied onto a support. The colored photopolymerizable composition layer is formed. Examples of the support which can be used in the present step include non-glass, sodium glass, Pyrex (registered trademark) glass, quartz glass, and the like used in a liquid crystal display device. A photoelectric conversion element substrate used for a transparent conductive film or an image sensor or the like, for example, a germanium substrate or a complementary metal germanium oxide semiconductor (CM〇S, C〇mplementary 〇 〇 心

Semiconductor) and so on. There are also cases where black stripes separating the pixels are formed on the substrates. Further, on the support, if necessary, it is possible to improve the adhesion to the upper layer and prevent the diffusion of the substance or the flattening of the surface of the substrate, and a lower coat layer may be provided. As a method of applying the colored photopolymerizable composition to the support, slit coating, ink jet method, spin coating, cast coating, or roll coating printing method can be used. The thickness of the coating film of the colored photopolymerizable composition is preferably (M Tao to 10 arrays), more preferably 〇2 _~5 _, and further preferably 〇.2 μιη~ When the color filter for a solid-state imaging device is produced, the thickness of the coating film of the colored light-combination composition is preferably 0.35 Å to the viewpoint of resolution and developability. Pottery, more preferably 〇4〇〇μιη. 143900.doc 201035049 The color photopolymerization of the support on the support έ μ, and the compound is usually carried out under conditions of f~11GC for 2 minutes to 4 minutes. Drying, forming a color photopolymerizable composition layer [exposure step] The exposure coloring composition layer formed in the coloring combination (4) forming step is exposed through a mask, and is exposed only to the exposure step. The coating film which is irradiated with light is partially hardened. 曝光 Exposure is preferably carried out by irradiation of radiation. As radiation which can be used during exposure, it is particularly preferable to use ultraviolet rays such as g-ray, h-ray, and ray. It is a high-pressure mercury lamp. The irradiation intensity is better than $ m. J/cm2~1500 mJ/cm2, more preferably 1〇^, and most preferably 10 mj/cm2~800 mj/cm2.

As other exposure light sources, you can also use ultra-high pressure, high pressure, medium and low dust mercury lamps, chemical lamps, carbon arc lamps, gas lamps, and metal functions.

Lights, visible and ultraviolet laser light sources, fluorescent lights, etc. Tungsten lamp, sun &lt;exposure step using a laser source&gt; In an exposure mode using a laser source, an ultraviolet laser is used as a light source. Laser Amplification by stimulated Emission 〇f Radiation (by excited mother. Using stimulated U-image generated in matter with particle inversion) and making interference and directional by amplification and oscillation of light waves More powerful monochromatic oscillators and amplifiers 'as excitation medium' have crystals, glass, liquids, pigments, gases. According to these media, solid Ray 143900.doc 35 201035049 can be used, liquid laser, gas laser A laser that has an oscillation wavelength for ultraviolet light, such as a semiconductor laser, etc. Among them, solid lasers and gas lasers are preferred from the viewpoint of laser output and oscillation wavelength. The wavelength of the ultraviolet light is preferably in the range of 300 nm to 380 nm, in terms of the photosensitive wavelength of the resist, and preferably the ultraviolet light of the wavelength in the range of 300 nm to 3 60 nm. Specifically, in particular, a Nd: YAG (Neodymium-doped Yttrium Aluminium Garnet) laser which outputs a large and relatively inexpensive solid laser can be preferably used. Three-harmonic (3 5 5 nm) or excimer laser XeCl (308 nm), XeF (353 nm). The exposure amount of the exposed object (pattern) is in the range of 1 mJ/cm 2 to 100 mJ/cm 2 . More preferably, it is in the range of 1 mJ/cm 2 to 50 mJ/cm 2 . If the exposure amount is in this range, it is preferable in terms of productivity of pattern formation. As an exposure apparatus using a laser light source usable in the present invention There is no particular limitation, and as a marketer, you can use Callisto (manufactured by V Technology Co., Ltd.) or EGIS (manufactured by V Technology Co., Ltd.) or DF2200G (manufactured by Dainippon Screen Co., Ltd.). It is preferable to use a device other than the above. In addition, a light emitting diode (LED) and a laser diode (LD, Laser Diode) can be used as the active radiation source, especially when an ultraviolet source is required. UV LEDs and UV LDs can be used. For example, Nichia Chemical Co., Ltd. has introduced a purple LED with a main emission spectrum with a wavelength between 365 nm and 420 nm. It is further shorter as needed. 143900.doc •36· 201035049 Wavelength At the time of the 'US Patent No. 6,084,25(), there are LEDs that emit active radiation between 300 nm and 370 nm, and other ultraviolet rays can be purchased to illuminate different ultraviolet regions. Radiation. In particular, the active radiation source system (Ultfa Vi〇let-Light £mitting Dj〇de, ultraviolet light emitting diode) is good, and the uv-LED has a bee wavelength at 340~370 nm. . Since the parallelism of the preparation and the external light field is good, the pattern exposure can be performed even if the lens is not used for 2^' during exposure. However, when the mask is used to expose the pattern, the linearity of the pattern becomes higher, which is more preferable. [Developing Step] After the exposure step, the development processing (development step) is subsequently performed, and the unexposed portion of the light in the exposure step is dissolved in the aqueous solution, whereby only the portion where the light is hardened remains. As the developer, an organic developer which does not cause damage in the circuit of the underlayer or the like is preferable. The development temperature is usually 2 (TC~3 (TC, 0 development time is 20 to 90 seconds. As a test used in the developer, for example, sodium hydroxide, potassium oxychloride, sodium carbonate, sodium hydrogencarbonate can be used. , sodium sulphate, sodium sulphate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl argon oxide, biliary test, mouth 嘻, bite, The W diazabicyclo[5 4 〇]_7_ eleven dilute compound is diluted with pure water to an aqueous solution having a concentration of 0.001 to 10% by mass, preferably 0.0 W% by mass. In the case of the developer of the above-mentioned aqueous solution, it is usually washed (rinsed) with pure water after development. 143900.doc -37- 201035049 Further, in the method for forming a colored pattern of the present invention, the colored light is carried out The polymerizable composition layer forming step, the exposing step, and the developing step may also include a hardening step of hardening the formed colored pattern by heating and/or exposure. Particle formation step, exposure step, and development step Further, if necessary, the hardening step) repeats only the required number of tones, thereby obtaining a coloring pattern containing a desired color tone, and producing a color filter. Here, as a method of forming the coloring pattern of the present invention, color is formed. In the coloring pattern of the color filter, the color photopolymerizable composition of the present invention is mainly described. However, the present invention is not limited to this aspect. For example, the color photopolymerizable composition of the present invention can also be applied. The formation of a black matrix that separates the colored patterns (pixels) constituting the color/light-measuring sheet. Specifically, a colored photopolymerizable composition of the present invention containing a black coloring agent such as carbon black or titanium black is used, as described above. The colored photopolymerizable composition layer forming step, the exposing step, and the developing step (and, optionally, the hardening step) are performed, whereby a black matrix (black pattern) can be formed on the substrate. The color filter thus obtained is used The colored photopolymerizable composition of the invention is characterized in that the colored pattern formed by the composition exhibits a higher adhesion to the support substrate and is resistant to development. Excellent in sensitivity, excellent in exposure sensitivity. 'The adhesion between the exposed portion and the substrate is good, and a pattern with a high resolution for the desired cross-sectional shape can be formed. Therefore, it can be preferably applied to a liquid crystal display device or a CCD (Charge). In the solid-state imaging device such as a Coupled Device, a charge-collecting device, etc. 143900.doc -38- 201035049 [Embodiment] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention The present invention is not limited to the following examples. The "parts" are based on the mass basis unless otherwise specified. The compound 1 as a specific ruthenium compound is synthesized by the method described below (Synthesis Example 1: Compound as a specific ruthenium compound) Synthesis of 1) 0 First, Compound A was synthesized by the following procedure. Ethylcarbazole (100_0 g, 512 512 m〇1) was dissolved in 26 〇 ml of chlorobenzene and cooled to 0. (: Afterwards, aluminum chloride (70.3 g, 0.527 mol) was added. Then, o-benzyl chloride (815 g, 0.527 mol) was added dropwise over 40 minutes, warmed to room temperature and stirred for 3 hours. Then, cooled to 0 ° After C, aluminum chloride (75.1 g, 0-563 mol) was added. 4-Chlorobutylphosphonium chloride (79.4 g, 0.563 m·l) was added dropwise over 4 minutes, warmed to room temperature and stirred for 3 hours. A mixed solution of 156 ml of a 5 mass% aqueous hydrochloric acid solution and 392 ml of distilled water was cooled to 〇°c, and the reaction solution was added dropwise. The precipitated solid was sucked, washed with distilled water and methanol, and recrystallized with acetonitrile. , Compound A having the following structure (yield 164.4 g, yield 77%) was obtained. [Chem. 4] 143900.doc -39- 201035049

Next, using Compound A, Compound B was synthesized by the following scheme. Compound A (86.5 g, 209 mmol) was dissolved in THF (tetrahydrofuran, tetrahydrofuran) 277 ml, 2,6-dimethylphenylthiol (30 g, 217 mmol) and sodium moth (3·0 g, 20.0 mmol), stir at 40 °; mix. Then, sodium hydroxide (8.66 g, 216 mmol) was added to the reaction mixture, followed by reflux at 40 °C for 2 hours. Then, after cooling to 0 ° C, a methanol solution of decyl alcohol (concentration: 28 wt%, 48 g, 249 mmol) was added dropwise over 20 minutes, and the mixture was warmed to room temperature and stirred for 2 hours. Then, after cooling to 0 ° C, isodecyl nitrite (29·3 g, 250 mmol) was added dropwise thereto over 20 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. The reaction solution was diluted in acetone (10 ml), and washed with a 0.1N aqueous solution of hydrochloric acid cooled to 0 °C. After extracting the organic phase with acetic acid, the precipitated solid was suction filtered with methanol. Then, recrystallization was carried out with acetonitrile to obtain Compound B (yield: 76.6 g, yield: 67%). 143900.doc -40- 201035049 [化5]

Then, using Compound B, Compound 1 was synthesized by the following scheme.

Compound B (46.4 g, 85 mmol) was dissolved in 230 ml of ethyl acetate, and triethylamine (10.3 g, 101 mmol) was added. Then, after cooling to 0 ° C, B-brewed chlorine (8.0 g, 102 mmol) was added dropwise over 20 minutes, and then the mixture was warmed to room temperature and stirred for 1 hour. The reaction solution was washed with 1 蒸馏 ml of distilled water cooled to 0 ° C, and extracted with ethyl acetate. After concentration under reduced pressure, the mixture was added dropwise to 100 ml of distilled water, and the precipitated solid was filtered off with suction, and then washed with 150 ml of isopropanol cooled to 0 ° C, and dried to obtain Compound 1 of the following structure (yield 49.7) g, yield 99%). [Chemical 6]

The structure of the obtained Compound 1 was identified by NMR (nuclear magnetic resonance). CH-NMR 400 MHz CDC13): 8.84 (s, 1H), 8.57 (s, 1H), 143900.doc -41 - 201035049 8.31 (d, 1H, J=8.0 Hz), 8.08 (d, 1H, J=8.0 Hz), 7.446-7.24 (m, 4H), 7.48 (q, 2H, 7.4 Hz), 7.09 (d, 3H), 3.10-2.90 (m, 4H), 2.50 (s, 6H), 2.35 (s, 3H) ), 2.17 (s, 3H), 1.48 (t, 3H, 7.4 Hz) Further, the structures of Comparative Compound 1 to Comparative Compound 3 were as follows. [Chemistry 7]

143900.doc -42- 201035049 Π Preparation of Colored Photopolymerizable Composition A-1] As a colored photopolymerizable composition, a negative-type photopolymerizable composition A-1 containing a coloring agent (pigment) was prepared. This composition produces a color light-emitting sheet. ~ (Synthesis Example 2) Synthesis of Resin (i-Ι) 6.4 g of n-octanoic acid, 200 g of ε-caprolactone, and 5 g of titanium (IV) tetrabutoxide were mixed, and heated at 16 Torr for 8 hours, followed by cooling. Polyester resin 〇1) was obtained up to room temperature. The synthesis process is shown below. [化8]

¢5 + HO^C7H15-n (Synthesis Example 3) Synthesis of Resin (J-1)

10 g of polyethyleneimine (SP-〇18, number average molecular weight coffee, manufactured by Nippon Shokubai) and polyester resin (i-1) l〇〇 g were mixed at 12 Torr. The crucible was heated for 3 hours to obtain an intermediate (J-ib). Thereafter, it was left to cool to 65, and 200 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) containing 3.8 of succinic acid was slowly added thereto and stirred for 2 hours. Thereafter, PGMEA was added to obtain a PGMEA1〇f4% solution of the resin. The resin 1) has a side chain derived from the polyester (i-1) and a carboxyl group derived from succinic anhydride. The synthesis process is shown below. 143900.doc • 43- 201035049 [Chemistry 9]

+polyethyleneimine -fcHzCH^N-}^ 〇 -fcH2CH2-N^-2 〇^^Ν^^〇·^*-〇7Η15-η

O

~|~CH2CH2—NH2*j~ -[-CH2CH2--NIG〇R^^〇^-C7H15.n Intermediate (J-IB)

°irH

•CH2CH2—NH- n+k

〇

〇 [CH2CH2一N^—||ΟΗ2〇Η2—Ν' Ο.

ΟΟ,Η,2~ί^ 〇 4ch2ch2-n^

°tH +CH2CH2—NH2 七 1 -|~CH2CH2_NH2-|~ -^-0Η20Η2·~-ι^^^

^7^15~n Resin (Jl) ll·Preparation of pigment dispersion-Preparation of dispersion of yellow pigment PY150 _ 40 parts of CI·Pigment Yellow 150 (PY150) as pigment (average _ impulse 6 〇nm) A mixture of the above resin (: Μ) 2 Ρ (} Μ ΕΑ ΕΑ ( ( ( ( 223 223 223 223 223 223 223 223 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 143 Mm) mixing and dispersing for 3 hours to prepare a pigment dispersion. - Preparation of a dispersion of green pigment PG36 _ will contain 40 parts of pigment pigment 36 (?()36) as a pigment (average particle size nm) and resin ( I_l) 2 nights (2 parts by solids) mixed night, mixed with a bead mill (zirconia beads 0.3 mm), dispersed for 3 hours to prepare a pigment dispersion. Using dynamic light scattering ( Micr〇trac buckle

UPA-EX150 (manufactured by Nikkiso Co., Ltd.) measured the average particle size of the pigment of the pigment dispersion, and the result was 25 nm. 1-2. Preparation of colored photopolymerizable composition a- (coating liquid) The component of the following composition A-1 was mixed and dissolved to prepare a colored photopolymerizable composition A-1. &lt;Composition A-l&gt; 26·1 part 14·3 Partpolymer (= copolymerization of 2.8 parts • Dispersion of green pigment PG3 6 • Dispersion of yellow pigment PY150 • Adhesive resin (benzyl methacrylate-曱) Acrylic acid molar ratio of 7: 3), weight average molecular weight of 5 〇〇〇) • Polymerizable monomer having 5 to 6 polymerizable groups in 1 molecule (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARADDPHA, dipentaerythritol 6:3 (mass ratio) mixture of hexaacrylic acid and dipentaerythritol pentaacrylate 3.54 parts • Photopolymerization initiator (Compound 1) 1.02 parts • Compound with epoxy ring (2,2-bis(hydroxymethyl) _1_butanol epoxy_4·(2-oxopentyl)cyclohexane adduct, manufactured by Daicel Chemical Co., Ltd. 0.480 parts EHPE-3150) 143900.doc -45· 201035049 • Polymerization inhibitor (pair Methoxyphenol) 0.001 8 parts • Surfactant (fluorine-based surfactant, trade name of Megafac F781-F 0.0334 parts • decane coupling agent (3-mercapto propylene oxy-trimethoxy decane) Propane) 0.320 parts • Solvent (PGMEA) 5 1.42 parts, calculate the weight average molecule And a number average molecular weight is gel permeation chromatography (GPC, Gel Permeation Chromatography) measurement of the following conditions.

Use column: TSKgel Multipore HXL-M (fine pore polydisperse linear column) Tosoh manufacturing detergent solution: THF Flow rate: 1 · 〇ml/min Temperature: 40 °C Detection conditions: RI system: High-speed GPC device type (TosohHLC -8220) [2. Production of color filter] 2-1. Formation of colored photopolymerizable composition layer The pigment-containing photopolymerizable composition A-1 obtained by the above treatment is a resist solution. After the slit was applied to a glass substrate provided with a black matrix of 550 mm×65 0 mm under the following conditions, vacuum drying (66 Pa) and prebake (80 ° C for 160 seconds) were performed to form colored light. Polymerizable composition coating film (coloring photopolymerizable composition layer). (Slit coating conditions) 143900.doc -46- 201035049 Clearance of the opening of the front end of the coating head: 100 μηι Coating speed: 150 mm/sec Clearance between substrate and coating head: 15 〇μηι • Coating thickness (dry thickness): 2 Μιη Coating temperature: 23°C 2-2·Exposure, development and subsequent 'The coloring of the photopolymerizable composition layer was exposed to 60 mJ/cm 2 using a proximity exposure machine (manufactured by Toray High-Tech Co., Ltd., LE5565A). Patterned. The entire colored photopolymerizable composition layer after the exposure was subjected to an inorganic solution (trade name: CDK-1, manufactured by Fuji Film Electronic Materials Co., Ltd.) in an i.0% aqueous solution (25 ° C). The ejection pressure was set to 0.2 MPa for 60 seconds and washed with pure water. 2-3. Heat treatment Thereafter, pure water was sprayed onto the colored photopolymerizable composition layer in a spray form to rinse the developer, followed by heating in an oven of 22 (rc for 1 hour (post-baking). 4. Thereafter, a blue colored photopolymerizable composition (CB_95〇〇L; manufactured by Fuji Film Electronic Materials Co., Ltd.) was formed into a colored pattern and further a red colored photopolymerizable composition (CR_95〇〇L;

Manufactured by Film Electronic Materials Co., Ltd. to form a colored pattern, vapor-deposited ITO (Indium Tin Oxides 'Indium Tin Oxide), and formed a spacer using a photopolymerizable composition (CSP-3210L; manufactured by Fuji Film Electronic Materia Co., Ltd.). Thus, a color filter having a color pattern of green 143900.doc -47 - 201035049 color, red, and blue on the substrate is obtained. [3. Performance Evaluation] - Colored layer development step, colored layer baking (post-baking) step - The same operation as the above-described step 2-1 is performed, and thereafter, a developing device (manufactured by Hitachi High-Technologies Corporation) is used. a 1.0% developer (a liquid obtained by diluting 1 part by mass of CDK-1 with 99 parts by mass of pure water, 25 ° C) using a potassium hydroxide-based developer CDK-1 (manufactured by Fuji Film Electronic Materials Co., Ltd.), The ejection pressure was set to 0.2 MPa, development was performed every 10 seconds between development times of 10 to 110 seconds, and it was washed with pure water (Example 3-1). Further, as shown in Table 1, the initiators were changed, and Examples 3 - 2 to 3 - 8 and Comparative Examples 1 03 - 1 to Comparative Examples 103 - 3 were carried out. [Table 1] Moon-defective compound or specific compound sensitizer, sensitizer, content, species, content, content, content, Example 3-1, Compound 1, 1.02 - - - - Example 3-2, Compound 1 0.51 A1 0.51 - - Implementation Example 3-3 Compound 1 0.51 A2 0.51 - - Example 3-4 Compound 1 0.51 A3 0.51 - - Example 3-5 Compound 1 0.51 - - F1 0.51 Example 3-6 Compound 1 0.34 A2 0.34 F1 0.34 Example 3 -7 Compound 1 0.34 A2 0.34 F2 0.34 Example 3-8 Compound 1 0.34 A2 0.34 F3 0.34 Comparative Example 103-1 Comparative Compound 1 1.02 - - - - Comparative Example 103-2 Comparative Compound 2 1.02 - - - - Comparative Example 103 -3 Comparative Compound 3 1.02 - - - - The sensitizers A 1 to A3 and the auxiliary sensitizers F 1 to F3 shown in Table 1 are the compounds shown below. 143900.doc -48- 201035049 [· ίο] ·· 4,4 bis(diethylamino)benzhydryl A2. —ethyl thiazepine g

A3 : Ο Ο Grab a must-open F2. 2-Siliconbenzone 11 Sawa F3: N-phenyl_2_mercaptobenzimidazole-Evaluation of development time _ Observe every 1 sec The development time conditions are collectively shown in Table 2. At ° °, secret development can be used, the middle of the so-called development time lower limit # in the use of the scene, the lower limit of the time is said to remove the non-pixel part. When the so-called temple is packaged at this time, there is no upper limit of the number of seconds. If the time is longer than the upper limit, it means that the development can be used or collapsed. Further, since the system '_' is used, the pixel is caused to be below the second limit, and because of the limitation of the % (Lang time), it is preferably below. Also, the development latitude indicates the difference between the seconds of the better 疋80 limit. y 0 The upper limit and the development time _ pattern linearity evaluation _ Using an optical microscope (evaluating the edge portion of the reflection. 、, :, 200 times), the edge portion of the coloring pattern is photographed, and an image like f /, X5 is observed. In the photo of the centimeter, the edge of the pixel is evaluated as "good", I43900.doc •49· 201035049 The part of the edge of the pixel (within the overall length of ι/3) is not a straight line, and the position is not present. The toothed person is rated as "Jiliang", and the edge of the pixel is rated as "slightly worse" if the 1/3 of the length of the pixel is not a straight line, or the part (the whole length is less than μ), and the edge of the pixel is Partially out of 1/4 of the overall length and the wrong tooth is rated as "poor. ~ The edge of the pixel pattern is in a straight line. When the edge of the pixel pattern, the beam 4 knife is due to residual film or undercut or other If the reason is jagged, it is necessary to increase the overlap with the black matrix, which will increase the width of the black matrix and cause the aperture ratio to decrease. Also, when the overlap with the black matrix is not increased, there is near the edge of the black matrix. No color layer Further, when the edge portion of the pixel pattern is in the form of a mineral tooth, there is a problem that the transparent electrode formed thereon is broken and the resistance value is increased. - Evaluation of defects - Using an optical microscope (with reflection Mode, 2 times) The edge portion of the pixel pattern was photographed and evaluated. In the photograph of 5 cm χ 5 cm, the edge portion of the plain was observed, even if a defect was observed (usually, the shape of the edge was formed in a half moon shape) Depending on the situation, there is also a case where the slender case is formed, and the width of the daily line is thinned from the periphery and is considered to be defective. Those who did not observe the defect were evaluated as "A". If a defect occurs, the portion will become blank and light leakage will occur. This is not 143900.doc -50- 201035049 [Table 2] Example 3-1 Example 3-2 Development time (sec) Pattern linearity defect. Lower limit upper limit latitude 30 80 50 slightly better - — A 20 80 60 A — Lean Example 3-3 Example 3_4&quot; Example 3-5 Example 3-6 _ 10 80 70 K~' A ~~ 10 70 60 ϊ _ A ~ A ~~ 10 70 60 10 70 60 Good - A ~ ~~ Xia Shi Example 3-7 10 70 60 Good _ ALA - Example 3-8 Comparative Example 103-1 ~~~ Comparative Example 103-2 Comparative Example 103-3 10 70 60 Good ~ 50 Π 80 30 Slightly B — A ~ A A — 40 80 40 Slightly worse “10 80 30 Poor — It can be seen from Table 2 that Examples 3_ 1 to 3-8 using the specific hydrazine compound of the present invention exhibit a large development latitude in pattern formation. Moreover, the straightness of the pattern is also good and the good developability does not cause defects. On the other hand, the comparative example of the specific bismuth compound is not used. (10)-丨~丨" The development latitude is small and the pattern is straight. The properties were also poor, and defects were produced in Comparative Example 1〇3_3, and the developability was poor. Further, in place of the compound i, the compound 2 and the compound 3 exemplified herein (each changed to a compound corresponding to benzoic acid, respectively, in the same manner as in the synthesis) were used instead of the compound i, and were prepared in the same manner as in the examples. The color light, the polymerizable composition' was evaluated in the same manner as in Example 3-1, and as a result, the same results as in Example 3-! were obtained. Further, among the pixels obtained in the example, the treatment was carried out for 3 minutes in an oven under the condition of 2, and as a result, AE* ab was 3 or less. (Example 4-1) A dispersion in which the green pigment PG36 was dispersed in the composition of Example 3-1, 143900.doc -51 · 201035049 was changed to a blue pigment PB15 ^ 6 (except that the pigment type was set to PB15: 6 and 29.4 parts of the same composition, using the same composition, using the same composition, and the dispersion of the yellow pigment PY15〇 was changed to the violet pigment PV23, except for the BYK_chemie company. The dispersion (manufactured by the same method as the PG36 dispersion, except that the pigment type is pv23 and the dispersant is made to Disperbyk-161 of BYK-Chemie Co., Ltd.), 115 parts, in the molecule The polymerizable monomer having 5 to 6 polymerizable groups was changed to NK Esta &amp; TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the exposure step was changed to the following, and the same procedure as in Example 3_ The colored photopolymerizable composition was produced in the same manner, and the same developability (development latitude, linearity of the pattern, and defect) as in Example 3_丨 was obtained. Good developability as in Example 3-1 was obtained. It From this result, it is understood that the excellent effect of the present invention is obtained even in the case of exposure using a laser exposure machine, similar to the exposure using a high pressure mercury lamp. (Exposure step) Using EGIS (V Technology Co., Ltd., YAG laser) The third spectral wavelength of 355 nm and the pulse width of 6 nsec were used as a laser exposure apparatus, and the surface of the colored photopolymerizable composition layer was irradiated with a pulse of about 丄mJ/cm2 by a photomask. 143900.doc -52 ·

Claims (1)

201035049. VII. Patent Application Range: 1. A colored photopolymerizable composition containing (A) a compound represented by the following formula (1), (B) a polymerizable compound, and (c) a colorant : [Chemical 1] An alkyl group of 1 to 4; wherein at least two of Υ1, Υ2 and Y3 are a methyl group; R1 is an alkyl group having 1 to 6 carbon atoms; and R2 represents a hydrogen atom or an alkyl group of carbon number 6; Represents a monovalent substituent, and η is an integer from 0 to 5. The color photopolymerizable composition of the present invention, wherein the content of the compound represented by the formula (1) is 〇. 1% by mass relative to the total solid content of the colored photopolymerizable composition. 30 mass 0 / 〇. The colored photopolymerizable composition of the invention, wherein the content of the (Β) polymerizable compound is from 5% by mass to 80% by mass based on the total solid content of the colored photopolymerizable composition. The color photopolymerizable composition of the above-mentioned item 1, wherein the amount of the above (C) colorant is 10% by mass based on the total solid content in the colored photopolymerizable composition. ~70% by mass. The color photopolymerizable composition of claim 1, wherein the (c) colorant is a pigment, and further contains (D) a pigment dispersant. 6. The colored photopolymerizable composition according to claim 5, wherein the above (9) pigment component is 143900.doc 201035049 7. 8. 9. The content of the powder is relative to the coloring 3 mass. /. ～40% by mass, the total solid matter in the conjugate composition is a method for forming a coloring pattern, comprising: forming a color photopolymerizable composition layer using the coloring polymerizable composition as claimed in claim 1A I π a step of exposing and patterning the gradation layer of the colored photopolymerizable composition to a pattern; and removing the unhardened colored photopolymerizable enamel composition portion. A color filter attached to a color pattern having a pattern formed by a method of requesting γ on a support or body. A liquid crystal display device 'having a color filter as claimed in claim 8. 143900.doc 201035049 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 143900.doc