TW200914995A - Color photosensitive composition for solid-state imaging device, color filter for solid-state imaging device and fabricating method thereof - Google Patents

Abstract

A color photosensitive composition for a solid-state imaging device, a color filter for the solid-state imaging device using the composition, and a fabricating method thereof are provided. The color photosensitive composition prevents pixel patterns from stripping under a developing process by using a low exposure dose even if the content of a colorant is high, and has good preserving age stability at room temperature or higher. The color photosensitive composition for the solid-state imaging device has a colorant ranging from 50 wt% to 80 wt% and a thermal polymerization inhibitor using a phenol series compound ranging from 1.0x10<SP>-5</SP) wt% to 1.0x10<SP>-3</SP> wt% with respect to total solid content. A fabricating method of the color filter for the solid-state imaging device is also provided.

Description

200914995 IX. Description of the Invention: [Technical Field] The present invention relates to a solid-state imaging device (Charge Coupled Device (CCD), Complementary Metal Oxide Semiconductor (CMOS)) a coloring photosensitive composition of a color image of a color filter (c〇i〇r filter) used by the user, and using the colored photosensitive composition

A color filter for a solid-state photographic element and a method of manufacturing the same. [Prior Art] The method of producing a color filter used in a solid-state image sensor is the same as the method of fabricating a color filter used in a liquid crystal display device, and is generally known as a dyeing method, a printing method, and a plating method. And pigment dispersion method. When the color filter is produced by the pigment dispersion method, the composition containing the lungs is coated on the substrate by a spin coater or a roll coater, and dried (4) Form a film. Dreaming The film was subjected to pattern exposure and development to form a colored halogen. Each of the colors is repeatedly subjected to the above operation, whereby a color filter L-spot can be formed, and a puncturing composition used in the method, for example, is known to be used for the test of a crystalline resin and a photopolymerizable monomer (_〇mer) and light. A polymerization initiator (Uega) photosensitive composition (for example, refer to Japanese Labor No. 7-140654 pure). In recent years, it has been desired to use color illuminators for solid-state photographic elements. For example, the technique of maintaining the bifurcation is disclosed, and it is revealed that 5 = 200914995 3 1 of the total _ component towel of the coloring sensation composition is added, and the resin is used to improve the = 专利 2 2 2 2 , , , , , , , , , , , !: The content of the second-conductive hardening component is relatively reduced, so 4: The problem of the sensitivity is remarkably lowered. The text ~ 疋 经 面 ' 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示 揭示:::: J ^ s-292566 . a - Bulletin, Japanese Patent Special Open 3_1775 Chuan Chea, if the coloring agent contains 詈槎古,目, 丨山 5 A and recent years of sound / asymmetry, by polymerization The effect of the decrease in sensitivity caused by the inhibitor increases the problem of the pattern peeling when it is sensitive. The development is performed with a low exposure first. [Summary of the Invention] Even if the title is made, the purpose is to provide a good固 摄 或 或 或 或 或 至 至 皿 皿 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 ^Coloring sensitivity group for photographic elements And characterized in that it is represented by a content relative to the total solid content, which contains 50 wt% and less than or equal to 8 wt% of the colorant and greater than or equal to 1 == ^10-3 Wt% of 纷(Ρΐ&quot;η 〇1) The heat of the compound is &lt;2&gt; The solid-state photographic element according to &lt;1&gt; is composed of coloring photosensitive composition 200914995

And the above coloring agent is a dye soluble in an organic solvent. The colored photosensitive composition for solid-state photographic elements according to the above-mentioned <1>, which further contains a resin which contains an unsaturated double bond and which is selected from the following formula ( 1) at least one structural unit and a thiol group in the first social group represented by any one of the formulas (3), and having 1;; ^, and feeding; 1.5 times or more than 1.5 times / 2,, and ° early (10) ratio (Mo R

II ο

A1—G R7 R5c-c^c 6 General formula (1)

1 2 R1丨? R1 110 CIR I Y I 2 G Formula (2) 200914995

General formula (3)

COOH General formula (4) In the above general formulae (1) to (3), A1, A2 and A3 each independently represent an oxygen atom, a sulfur atom or -N(R21)-, and R21 represents a hydrogen atom or may have a substituent. alkyl. G1, G2 and G3 each independently represent a divalent organic group. X and Z each independently represent an oxygen atom, a sulfur atom or -N(R22)-, and R22 represents an alkyl group which may have a substituent. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent or -N(R23)-, and R23 represents a hydrogen atom or an alkyl group which may have a substituent. Ri, R2, R3, R4, R5, r6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R8, R19 and R20 each independently represent a monovalent substituent . Further, in the above formula (4), RA represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and RB represents a divalent bond group. The coloring photosensitive composition for a solid-state imaging device according to the above-mentioned item, wherein the weight average molecular weight of the resin is 30,000 or more and 300,000 or less. The photosensitive composition for solid-state photographic elements according to any one of <1> to <4>, which further comprises an oxime initiator. The coloring photosensitive composition for a solid-state image according to any one of the above-mentioned items, wherein the content is more than 1.0 wt% with respect to the total solid content. 4〇.〇wt% of a photopolymerization initiator. &lt;7&gt; A method of producing a color filter for a solid-state photographic element, comprising: coating a coloring photosensitive composition for a solid-state photographic element according to any one of &lt;1&gt; to &lt;6&gt; a step of forming a silky color-sensitive composition layer on the branch (four); and exposing and developing the colored photosensitive composition layer by a mask to form a pattern on the support. &lt;8&gt; A color filter for a solid-state photographic element, which is formed by using the colored photosensitive composition according to any one of &lt;6&gt;. [Effect of the Invention] According to the present invention, it is possible to provide a method in which the content of the coloring agent is high, and the amount of exposure can suppress the peeling of the alizarin pattern during development, and the stability over time is good when stored at room temperature or above. A coloring photosensitive composition for a solid-state imaging element; and a color filter for solid-state photography using the colored photosensitive composition and a method of manufacturing the same. The above and other objects, features, and advantages of the present invention will become more apparent. [Embodiment] The present inventors conducted a research on a color-sensitive photosensitive composition suitable for the production of a solid-state photographic element in a color-light-emitting state, and as a result, found a color-sensitive photosensitive composition having a relative solid content. It is indicated that the polymerization inhibitor containing 10 200914995 has a coloring agent of 5〇wt% or more and 8〇 or less and a phenolic compound of 1^0x10-5 Wt% or more and less than or equal to i 〇xl〇-3 wt%. Therefore, even if the content of the coloring agent is high, the low-exposure crucible can be used to suppress the peeling of the pixel pattern during development, and the stability with time is good when stored at room temperature or above. <Coloring photosensitive composition> The coloring photosensitive composition of the present invention (hereinafter sometimes referred to as "the present invention group") contains at least one of a predetermined amount of the (A) coloring agent and the pre-tanning amount (B) selected from the copious compound. At least one of the thermal polymerization inhibitors may be further composed of other components as needed. Hereinafter, each component constituting the colored photosensitive composition of the present invention will be described in detail. (A) colorant

The colored photosensitive composition of the present invention contains a coloring agent of 50% by weight or more and 8% by weight or less based on the total solid content. In the present invention, the "total solid content" means all components other than the solvent contained in the coloring photosensitive composition. The above coloring agent can be used without any particular limitation, and the known pigments and dyes used in the color filter are used. ~Pigment~ The pigment which can be contained in the coloring photosensitive composition of the present invention includes various inorganic pigments and organic pigments which are known in the prior art, and is preferably a material having a high light transmittance. The pigment having a high light transmittance, if used in a red &amp; (Red) filter, refers to a pigment having a small absorbance of 600 nm to 700 nm; if it is used for green (G) filtration, The pigment in the optical device refers to a pigment with a small absorbance at 525 nm 200914995 ～575 nm; if it is used for a blue filter, it refers to a pigment with a small absorbance at 425 nm to 475 nm. . Examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include iron, cobalt, aluminum, cadmium, copper, titanium, and titanium. a metal oxide such as magnesium, chromium, zinc or antimony or a composite oxide of the above metal. Examples of the organic pigment include: f ' CI pigment yellow ll, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167 , 180, 185, 199; c. I. Pigment Orange 36, 38, 43,71; CI Pigment Red 81,105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270 ; CI Pigment Violet 19, 23, 32, 39 ; CI Pigment Blue 1,2, 15, 15:1, 15:3, 15:6, 16, 22, 60, 66 ; ( c I. Pigment Green 7,36,37; CI Pigment Brown 25, 28; CI Pigment Black 1, 7; carbon black, etc. In the present invention, 'in particular, it can be preferably used in the structural formula of the pigment. A pigment having a basic N atom. These pigments containing a basic N atom exhibit good dispersibility in the colored photosensitive composition of the present invention. The reason for this is not very clear, and it is presumed to be due to the affinity of the polymerizable component and the pigment. Effect of high and low 12 200914995. The pigments which can be preferably used in the present invention include the following pigments, but the present invention is not limited to these pigments. CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 18 0, 185 ; c. I. Pigment Orange 36,71 ; CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264 ; CI Pigment Violet 19, 23, 32 ; CI Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66; CI Pigment Black 1. These organic pigments may be used singly or in combination of two or more. By combining two or When two or more types are used, the color purity of the pigment can be improved. For example, when the colored photosensitive composition of the present invention is used to form a colored pattern of a color filter, it is preferable to use two or more kinds of pigments in combination. In this way, the color purity of the colored pattern of the color filter can be further improved. Specific examples of the combination of the pigment and the pigment are as follows. For example, 'the red pigment can be enumerated. · Anthraquinone-based pigment and peryiene are used separately. And a diketopyrrolopyrrole pigment; and at least one of the above red pigments and a disazo yellow pigment, an isoindoline yellow pigment, Quinophthalein (quinophthal〇ne) is yellow And at least one of them perylene-based red pigment combination. 13 200914995 The above-mentioned quinone-based pigments include, for example, C I. Pigment Red 177, and examples of the above-mentioned fluorene-based pigments include CL Pigment Red 155 and CI•Pigment Red 224, and examples of the diketoppyrrolepyrrole pigments include c. Pigment red 254. In the present invention, in terms of color reproducibility, a combination of Huixikun pigment, an anthraquinone pigment, or a diketopyrroloxime 0-pyroline pigment and C., Pigment Yellow 139 is preferred. ' The weight of the red pigment and the yellow pigment in the above combination is preferably 100/5 〇 to 100/5. By adjusting the above weight ratio to /5 or less, light transmittance of 400 rnn to 500 nm can be suppressed, so that color purity can be further improved. Further, by adjusting the above weight ratio to 1 〇〇/5 大于 or more, the dominant wavelength can be prevented from being biased to a short wavelength, thereby further reducing the deviation from the target color of the National Television System Committee (NTSC). . The above weight ratio is particularly preferably in the range of 1 〇〇 / 3 〇 to 100/10. Further, when two or more red pigments are combined, the respective content ratios can be adjusted to match the chromaticity. Further, as the color pigment, a phthalocyanine halide pigment can be used alone, and the pigment and the disazo-based yellow pigment, the quinophthalone-based ka-color pigment, and the az-methine (az-methine) system can be used. A yellow pigment or a different color is used as a yellow pigment for mixing. For example, a combination of the above is preferably C.I. Pigment Green 7, 36, 37 and c. L Pigment Yellow 83, c. L Pigment Yellow 138, C. L Pigment Yellow 139, C. I. Pigment Yellow 150 , a combination of CI Pigment Yellow 180 or CI Pigment Yellow 185. Green The weight of the green pigment and the yellow pigment in the above combination is preferably 100/150 to 100/5 ', particularly preferably in the range of 1〇〇/12〇~1〇〇/3〇. 14 200914995 Blue pigment can be used alone as a phthalocyanine pigment, and a combination of this dioxazine and purple pigment. For example, the mixture of L Pigment Blue 15:6 and C.I. Pigment Violet 23 is good.疋· The weight ratio of the blue pigment to the violet pigment in the above combination is preferably 100/10 to 100/1 Å, and more preferably 100/10 to 100/1. Further, the pigment used in the coloring photosensitive composition of the present invention for forming a color, black matrix may be made of carbon, titanium carbon, iron oxide, titanium oxide or the like. Group t, compared to the combination of carbon and titanium carbon. Further, the weight of the carbon and the titania in the above combination is preferably in the range of 100/60 to 100/1. When the coloring sensitizing composition of the present invention is used for a color grading device = that is, a pigment-sub-granule # self-color unevenness or contrast (a coffee ship) viewpoint = it is preferably less than or equal to (10) nm, and further, self-dispersion is stable Sexual view ', 曰 consider 'good is A Yuke 5 nm. Lai's - wire diameter is better 疋 5 nm ~ 75 nm ' Further preferably 5 nm ~ 55 is 5 nm ~ 35 nm. The primary particle diameter of a few or a good pigment can be measured by a known method such as an electron microscope, and the pigment is preferably selected from the group consisting of an anthraquinone, a sulfhydryl azo, a benzylidene, and a flower. A pigment in the cyanine system, the diketopiperyl group, and the ketone system and the phthalocyanine system. ~ Dye ~ In terms of forming a finer pattern, the coloring agent of the present invention is preferably a dye. In particular, in view of the fact that the fine pattern can be formed into a rectangular shape, it is preferable that the coloring agent is soluble in the coloring agent, all of which is soluble in the organic solvent, and more preferably, the dye has polymerization inhibition property, =4. Furthermore, it is generally good. When the coloring agent is a dye, the stability is good with time. The dye can be used in the previously known Bikai 64-9G403, Japanese specials, such as the Japanese Patent Special Japanese Machine Kaiping (4) &amp; Temple = 64·911 (10), ί

No. Gazette, daily turn 25922n?\Japan specializes in Kaiping 6_Wrist 4 material, Mingkui ^Zhoudi 07 5 Tiger, US Patent 4,808,501 2t·, No. specification, US patent No. ^ stomach Japanese judgment Ping 6·3 · No. bulletin, etc. • No, prime. In terms of chemical structure, a triphenylmethane ^ _ ^ café / coffee system can be used, a brewing system, a sub-base system, an oxygen sigh (a scorpion (4) system, a cyanine system, a phenothiazine system, a pyrrole a dye such as pyrrolopyrazole azomethine, xanthene, indigo, benzopyrene, benz〇pyran, indigo, etc. Preferably, the pyrazole azo system, the anilinozo system, the pyrazolotriazole azo system, the pyrid 〇 azo (pyrid〇ne azo) system, 蒽» Anthrapyridone dyes. In addition, direct dyes, basic dyes, mordant dyes, acid dyes, azoic dyes, dispersions Disperse dyes, oil soluble dyes, food dyes, and/or derivatives of these dyes can also be effectively used. 16 200914995 &lt;Acid dyes&gt; Description: The coloring of the photosensitive group of the present invention is a color group It has the solubility in the % sulfhydryl group or the 2 organic solvent-based hydrating solution, the salt form H with the secret compound, the absorbance, the interaction with other components of the hair surface of the hair, the light resistance, the heat resistance, etc. Performance to choose.

Specific examples of the acid dye are listed below. However, the invention is not limited to these dyes. For example, acid alizarin violet N; acid black 1,2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; acid chrome violet K; Acid fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 ; acid lamp Orange ) 6, 7, 8, 10, 12, 26, 50, 51,52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173 ; acid red 1,4, 8,14,17,18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 17 200914995 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107 ; direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 ; direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95 , 96, 103, 104 ; direct blue 57, 77, 80, 81,84, 85, 86, 90, 93, 94, 18 200914995 95, 97, 98, 99, 100, 101, 106, 107 , 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172 , 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244 , 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293 ; direct green 25, 27, 31, 32, 34, 37, 63, 65 , 66, 67, 68, 69, 72, 77, 79, 82 ; mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50 ,61,62, 65 ; mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42 , 43, 47, 48 ; mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33 , 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 ; mordant violet 2, 4 , 5, 7, 14, 22, 24, 30, 31, 32, 37, 40,41,44, 45,47, 48,53,58 ; mordant blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19,20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61,74, 77, 83, 84 ; mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53; food yellow 3; and derivatives of these dyes. 19 200914995 Among the above acid dyes, preferred are: Acid Black 24; Acid Blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324:1; Acid Orange 8, 51,56,74,63; Acid Red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217, 249; Acid Violet 7;

Acid Yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243; Acid Green 25; Dyes and derivatives of these dyes. As the derivative of the acid dye, an inorganic salt of an acid dye having a sulfo group or a carboxyl group, a salt of an acid dye and a nitrogen-containing compound, and/or an amide compound can be used, and if it is soluble in the composition of the present invention, Special restrictions. The derivative of the acid dye can be selected in consideration of the organic solvent or the solubility, the absorbance, the interaction with other components in the composition of the present invention, the light resistance, the heat resistance and the like. It is a salt of an acid dye and a nitrogen-containing compound and a guanamine compound. To form a salt or a chelating compound with a nitrogen-containing compound, ====;: a solution containing a salt and a nitrogen-containing compound that forms a salt with an acid dye, and a guanamine with an acid 20 200914995 dye The nitrogen-containing compound of the bond may take into consideration the solubility of the salt or the guanamine compound in the organic solvent or the developer, the salt formability, the absorbance and color value of the dye, and the composition of the present invention. The interaction of other components, the heat resistance of the colorant, and the light resistance are selected. In the case of selection from the viewpoints of absorbance and color value, the above nitrogen-containing compound is preferably a compound having a molecular weight which is only likely to be small, and among them, a compound having a molecular enthalpy of 3 Å or less is preferable, and a molecular weight of less than 3 Å is preferable. A compound equivalent to the composition, particularly preferably a compound having a molecular weight of 250 or less. The molar ratio (hereinafter referred to as η) of the nitrogen-containing compound/acidic acid in the salt of the acid dye and the nitrogen-containing compound is determined to be the value of the acid dye knife = the relative ion (eGuntei > iQn) The value of the molar ratio of the compound ' can be selected from the salt forming conditions of the acid dye and the nitrogen-containing compound. Specifically, according to the acid (four) energy base number in the acid dye, the value between g &lt; i^5 can be comprehensively considered in the solubility in the clear liquid, salt formability, absorbance, and the present hair

The need for sex, the other components of the cockroach, the resistance, resistance, heat resistance, etc. must be selected. When the selection is made from the viewpoint of self-absorption, the value of &lt;2 32 Q&lt;n$4·5 is preferably 0. The value of the value is particularly good is the value between G&lt;d5. In particular, in the case of a coloring agent for coloring a photosensitive domain, a donor of more than one nitrogen bond is produced in the dye (" is particularly well described in the Japanese. Specific examples of the dye described above can be cited for ί 专用 2006-243040 In the dyes of the coloring photosensitive composition of the present invention, the coloring agent of the coloring photosensitive composition of the present invention is preferably in the form of a dye which is soluble in organic (4)::, and heat resistance: : At least - kind of organic spray phthalocyanine is available if it is available. Children's scales _, can be suitable for the benefit of two, there are some of the materials can be listed:

Newspaper, 曰本专利特门;报,曰本本专利开开6-51115号, especially the good material described in the H-opening 6_194828 bulletin =:: 素素=中之鸣料 γ The pigment compound represented by (I): (色素): The pigment compound represented by ί? 2 will be described. The pigment compound of the following formula is not / ^

Heat resistant compound. ‘also 卞科’疋_ meets high lightfastness and high

The above formula (I) formula (I)

Rcl represents a halogen chop, a lipid group, 22 200914995 aryl, a heterocyclic group, a cyano group, a county, an amine aryl group, a thiol group, a thiol group, a hydroxy group, an aliphatic oxy group, a heterocyclic oxy group, an aliphatic thio-based thiol group, an N-alkyl decylamino group, an amine (tetra) ylamino group, an amine fluorenylamino group (SUlfamoylamin oxime), an aliphatic oxo-oxycarbonylamino group, Aliphatic sulfonylamino group=two η:thio group, erythromylidene sulfonyl group, arylsulfonyl group, amine sulfonyl group, % group, &amp; imine group, or heterocyclic thio group to form 6 A non-golden divalent atomic divalent metal oxide or a divalent metal hydrogen metal atom or a substance necessary for the ring of the member. (10) indicates a ruthenium, a ruthenium or a divalent metal chlorination plus h or an integer of 1 to 5. 4 of the same as C. Among them, at least one of '(3) means 1 to 5 2 = and multiple Rci can be the same or different. -1, cr2 cr3 and cr4 represent 〇 or i, and satisfy cr ^ Chains, "aliphatic groups" are either saturated or non-existent, for example, unsubstituted, or you can take a piece of beauty, "= any of the private" can be in the ring and have Deuterated "Heterocyclyl" means that the heterocyclic moiety thereof has a hetero atom (for example, a nitrogen atom, a sulfur group ' may be a saturated ring or an unsaturated ring, and may be unsubstituted or may be In the substituted formula (1), the "substituent" is a substitutable group. 23 200914995 Examples thereof include an aliphatic group, an aryl group, a heterocyclic group, an oxygen group, an azo group, a fluorenyl group, and a silky group. Lipid oxymethanthine, ethoxylate, aryloxy-based, aryl-based, silk-based, hetero-, hydroxy, aryl, heterocyclic Bismuth oxide & sulfhydryl, sulfonamide, ^ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Amine t,, "(sulfinyl), aryl argene 4 base = " Earth sulphate, heterocyclic thio, hydroxy, cyano, sulfoamino, aryloxyamino, amidinoamine, amine sulfonate A thiol group, a halogen atom, an amine sulfonylamine sulfhydryl group, an amine carbaryl sulfonyl group, an aliphatic phosphinyl group (GxyphGsphinyl), a diaryloxyphosphino group, etc. In the general formula (I), the RCl table _ atom, fat, group, aryl, heterocyclic, cyano, thiol, amine aryl, aliphatic oxycarbyl, aryloxycarbonyl, fluorenyl, hydroxy, aliphatic oxy, aromatic Oxyl, decyloxy, amine methyl methoxy, heterocyclic oxy, aliphatic oxycarbonyloxy, N-alkyl decylamino, amine mercaptoamine, amine sulfonylamino, lipid = ethoxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfonylamino group, f-sulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, aryl sulfonate The sulfonyl group, the sulfo group, the sulfonium iodide group or the heterocyclic thio group. The halogen atom represented by the above Rq may, for example, be a fluorine atom, a gas atom or a bromine atom. The aliphatic group represented by the above Re! may be unsubstituted or may have 24 200914995, the substituent 'may be saturated' or may be subtracted, and may be cyclic, and the preferred total carbon number of the lanthanum is 1~ 15 aliphatic groups. For example, a mercapto group, an ethyl group, a vinyl group, an allyl group, an ethynyl group (~(1), an isopropenyl group, a 2-ethylhexyl group, etc. may be mentioned."

The aryl group represented by the above RCl may be unsubstituted or substituted, and is preferably an aryl group having a total carbon number of 6 to 16, more preferably an aryl group having a total carbon number of 6 to 12. For example, a phenyl group, "Schottylphenyl (4-nit_enyl), 2 · Weiphenyl, 2, chlorophenyl, 2,4_^ dimethylphenyl, 2 methylphenyl, 4_foxy Phenyl, 2, nonyloxyphenyl, 2-decyloxycarbonyl-4-nitrophenyl, etc. The above-mentioned % represents "the base can be a surface, and can also be unsaturated, ^ is the total carbon number The heterocyclic group of 1 to 15 is more preferably a heterocyclic group having a total carbon number of 3 to 1 Å, and examples thereof include a 3_D ratio of 3_pyridyi, 2_pyrimidinyl, and a pyridyl group. Generation t ^ you 1), etc. X 'the above heterocyclic group can also have more

The above-mentioned Rei indicates that the conversion can be unsubstituted, and it is also possible to have an amyl group, preferably an amine f-group having a total Wei of from 1 to 16, more preferably an amine group of from 1 to 12. For example, sulphate, carbamoyl, decyloxyethylamine, decyl, and the like. A fatty acid represented by RGl can be unsubstituted/, has a substituent, can be saturated, or can be saturated, can be $= 2 total carbon number of 2~16 An aliphatic oxy group having a carbonyl number of 2 to K). For example, a = 25 200914995 group, a butoxy group, etc. are mentioned. Replace i: good: generation, can also have a secret A 7 material oxygen base, better wait for ‘, ,, ~ 5 aryloxy record. For example, the thiol group represented by phenoxy can be aliphatic, and r ΪΪ also Sf: more substituted, indicating that the aryl group has a substituent, which may be saturated or Any of the unsaturated ones is better: ίΪί: The shouting is better than the brewing base with a total carbon number of 2 to 15 ((10) γ υ, ΐ 的 酿 。. For example, 乙转—methyl乙县(pivaloy1 ), benzoic acid (benz〇yl) temple. Further, the above fluorenyl group may have a more substituent. The thiol group represented by RGl may be unsubstituted, may have a family oxygen, or may be unsaturated. Further, it may be a cyclic group. The aliphatic carbon group having a fatty carbon number of 1 to 12 is more preferably an oxyethoxy group, a phenoxyethoxy group or a thiophenoxyethoxy group P. The aryloxy group which may be represented may be unsubstituted or may have an aryloxy group having a total carbon number of 6 to 18, more preferably a total carbon number ', and an aryloxy group of hydrazine. Phenoxy group, &quot; phenoxy group, etc. The decyloxy group represented by Rc can be unsubstituted, and the substituted oxy group having a total carbon number of 2 to 14 can be substituted with i, and more preferably Carbon number oxy group Base, etc. Bar·B, methoxyethyl 26 200914995 The above-mentioned amine methyl substituent, preferably the total carbon number is unsubstituted, or may have a total number of breaks i The amine of ～12 is an alkoxy group of 16 or more, more preferably a ethoxylated group, and the diisopropylamine oxy-oxyl group is, for example, a hetero group represented by the above RC of dimethylamine. It is a total carbon number which is substituted by ^, and may have a heterocyclic oxy group of #-胃1, which has a carbon number of 3 to 1 ,, more preferably a total of the above-mentioned Re, a group of bases, a group of methyl groups. Bite oxy group, etc. = yloxy group, more preferably total carbon number; = several benzyloxy group -, (deutero) butoxy group and St1, the mu group of the amine group can be unsubstituted It is also possible that the total carbon number is 3 to 15 ❺ &amp; silk-based amine oxime and Μ ΙΑ 为 为 为 为 为 为 为 为 。 。 。 。 。 。 。 。 其 其 其 其 其 其 其 其 其Oxyethyl benzhydrylamino group, fluorenyl-methylmethoxyethyl hydrazino group, etc. The above-described amine carboxymethylamino group represented by RCl may be unsubstituted or may have a substituent of 'good. The total number of carbon atoms is 丨, the total number of carbon atoms is 丨An amidoxime group of ～12, for example, n, n_, methylamine, alkanoylamino, N-fluorenyloxyethylamine, formate, and the like. Soil 27 200914995 Female said jRCl The amine hydrazide group represented by the amine may be uncapped, and has a substituent. It is preferred that she does not replace the amine, or that it has a good hindrance of the amine gamma amine group. In the case of a methylamine, for example, Nn=ΐ!, N,N-diethylamine, hydrazino group, etc. may also be present as a fatty acid base. Substituted, &quot; base, preferably a few amino groups with a total carbon number of 2 to 15, more preferably her 5 _

base. For example, an aliphatic oxy group amine group of: = 10 is exemplified. τ 丝 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县Amine oxime; ~ aryloxy amino group having a carbon number of 7 to 15. For example, it can be exemplified by the silky m-siloxyamine and the like. The aliphatic sulphate amino group represented by the escape RCl may be unsubstituted, and may also be saturated or unsaturated, and may also be cyclic. Two =, 醯 胺 胺 车 车 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的 好的For example, a carbaryl group, a butyrylamino group, etc. are mentioned. The aryl group of the above Rei can be unsubstituted, and can also be substituted. The preferred one is a total carbon number of 6 to 15 and a better total carbon number of 6~ An arylheteroalkyl group of 12. For example, a benzocarbylamino group, a &quot;nonylamino group, etc. are mentioned. The aliphatic thio group represented by the hydrazine may be unsubstituted, may have a soil, may be saturated, may be unsaturated, and may also be cyclic. Fat 28 200914995 The group thio group is preferably an aliphatic group having a total carbon total hindrance of ho: 16 _ an aliphatic thio group, more preferably a thio group, an ethoxyethyl thio group or the like. , now based. For example, an aryl furnace group represented by a methylthio group or a above Rc] may be mentioned, and it is preferred that the total hindrance is a substituted arylthio group having a substitution of 6 to ,, preferably. It is a total carbon number sulfur group and the like.歹 · 本 本 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Further, for example, the oxygen may be exemplified by a repeating substituent, and may have a 4-tert-butylbenzenesulfonyl group 'T歹'. The present fluorenyl group and the hydrazine group are represented by Amine Mei Ke: After taking: 2: Wait for the base amine Guji. For example, an amine surface group, a dimethyl group is a total two: a step-enhanced ring, a preferred phthalic acid imine group, etc. / u imine group - the heterocyclic thio group represented by the above Rci Substituted, can also have taken 29 200914995 5~7 member ring 'better is a total carbon number of 1~2G heterocyclic bowl meaning better is the total carbon number is 1 ~ dip her π Mu 亘 to spot / base ^ «. The hydrazine thiol. For example, 3-indenethio group, 3-pyridylthio group and the like can be mentioned.夭°南 In the general formula (I), Zci represents a 6-member 戸, a necessary non-metal atom group together with a carbon atom, and the four ZCls may be the same or different. The 6-membered ring formed may be any of a silk ring or a heterocyclic ring, and may be further modified, and the ring of the added ring may have a more substituent. For the 6 g ring, for example, the ring, the ring, the Cycl〇hexene ring, the naphthalene ring, etc., are suitable for the 6-ring ring. In the above formula (I), M represents two hydrogen atoms, a divalent metal precursor, a divalent metal oxide, a divalent metal hydroxide or a divalent metal chloride. For example, v〇, Ti〇, Zn, Mg, illusion, Sn,

Rh, Pt, Pd, Mo, Μη, Pb, Cu, Ni, Co, Fe, A1C1, Ιηα,

FeCl, TiCl2, SnCl2, SiCl2, GeCl2, Si(OH)2 and H2, etc., and the M is VO, Zn, Μη, Cu, Ni or Co is suitable.

In the above formula (0, 'em represents 0, 1 or 2 (preferably 〇), cn represents 〇 or an integer of 1 to 5 (preferably 〇 or 1), and 4 cn in the molecule may be the same, Alternatively, one of (3) represents an integer of 1 to 5, and when a plurality of cns are present in the molecule, a plurality of rCis may be identical to each other 'may be different. Also 'crl, cr2, cr3, and cr4 represent 0 or 1, satisfying Cri + cr2 + cr3 + cr421. Among them, it is preferred that cri + cr2 + cr3 + cr4 is a state of 3 wei 4. In the above-mentioned pigment compound represented by the general formula (I), it is preferred to describe the general formula (1) 1) The pigment represented. 30 200914995

(Rc:) cp

In the above formula (1-1), RC2 represents a substituent, and a group which may be substituted may be mentioned, and a group of ς = in the "substituent" term described above may be mentioned. Is an aliphatic group, an aryl group, a heterocyclic amino group, an aliphatic oxy group, Hi, # stomach stomach I, its m μ heteroporous group, an aliphatic oxy group base group, a ruthenium, a miscellaneous Epoxycarbonyl, amine sulfhydryl,

Base, sulfonamide, aliphatic hydrazine, "fat private amine, guanqi (4) base group continuation of amine base, aliphatic aliphatic", amine f _ yl 'amine, amine guamine , 醯 醯 N-alkyl fluorenylamino group, 妒 ^ ^ # 甘 尺 疋 疋 私 私 私 私 私 私 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 私 私 私 私 私 私 私Base, silk, (four) atom. An integer of 〇~4. When the positive number of the eight Cr2 Cp + Cr3, cp + cr4 is greater than the number of % in the knife, the multiple shame phases 31 200914995 may be different. Further, Re, Μ, cm, cn, and eri, cr2 cr3 &amp; cr4 in the formula (1-1) have the same meanings as in the above formula (I), and are preferably separated from the above formula (1-1). Among the dye compounds represented by the formula (1-2), a dye represented by the following formula (1-2) is more preferable.

General formula (1-2) In the above formula (1-2), the meanings of 'RC1, rC2, μ, cm, cn and crl, cr2, Cr3 and cr4 and the above formula (I) and (I_〇) Similarly, the preferred embodiment is also the same. Further, cq in the formula (1_2) represents 〇 or J. Further, 酞月月 &amp; has a condensation on the outer side of the tetraazap 〇rphyrin skeleton. The structure of four benzene rings, each of which has four sites (carbon atoms) into which a substituent can be introduced, and the above formula (〗 2-1) is far from the tetraazaindene of the respective benzene rings 32 200914995 (p In view of the fact, the cyano group is more effective in exerting the effects of the present invention, and the RCI is a dentate atom, an aliphatic group, or an aliphatic group. Oxy,::di:oxy 3, aryloxycarbonyl, hydroxy, yl, amine, hydrazone λ 'Ί, _A, fluorenyl carbonyl oxy, aliphatic = ^ = ___ylamino, amide, fat Continuation: Amino group: aliphatic thio group, aromatic smear sample; base: sub = brewed "di 醯 = county, aliphatic oxy, aliphatic aliphatic arylamino group, sulfhydryl amine, lipid = = County soil, ^ base ~ brewing base, The sulphate, the sulphate or the sulphate is in the form of the above-mentioned Rel, which is an amine π group, a fatty weiji group, an i amine: a fat ΐ oxy group, an amine mercaptoamine group, a fat. : '. The same can effectively exert the effect of the present invention in the same manner as the hydroxy group of the sulfonium group, the quinone imine group or the uranium group, and the above is the aliphatic group. More preferably, N•alkyl thiolamino, ς' milyl, aliphatic oxy, aliphatic diabase, aliphatic thio, thio, benzyl, silk or halogen atom, more preferably The aspect of the R aliphatic group or the halogen atom. Similarly, in terms of being more effective in the effect of the present invention, it is preferred that the above-mentioned state is more effective to exert the effect of the present invention. On the other hand, it is better that the two are 33, 2009, 14,995, and the above M is VO, Μη, Co, Ni, ΓΊι, 7 ·+, 'good, this M is the state of VO, Co, Cu*7'

The best of A Cu m M . or n is this M-like. Also, it is better to -. The way. Further, a better 疋(3) is a 1 or 2 aspect, and it is better if it is! The way. In order to effectively exert the effect of this judgment, the above j = good is: the above % is a functional atom, an aliphatic =,, an amine, a mercapto group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, f light base, aliphatic oxy group, amine methyl oxime hair, m-heterowei group, aliphatic oxyamine group, amine sulfonylamino group, aliphatic oxycarbonyl, sulphate An aryl group, an aliphatic thio group, an alicyclic group, an aliphatic diabase group, an aryl sulfhydryl group, an amine fluorenyl group, a quinone imine group or a sulfo group, wherein the above oxime is vo, C〇, Cu or ζη, the above is called 〇 'the above cm is 〇' and the above cn is! The appearance, ♦, and better 疋. The above Re! is an aliphatic group, an amine methyl group, an aliphatic oxy group, an aryloxy group, an aliphatic oxy group, an aliphatic oxy group Oxyl, amine mercaptoamine, amine decylamino, aliphatic oxyamino, aliphatic sulfonylamino, selylamine, lipid lysyl, fluorenyl, Aminesulfonyl, quinone or sulfo group, the above M is v〇, c〇, 戋

Zn, the above cq is 〇, the above cm is 〇, and the aspect of the above (3) is i. In particular, from the viewpoint of the effects of the present invention, it is preferable that the above Re! is an aminomethyl sulfonyl group or an aliphatic oxy group. a carbonyl group, an aliphatic oxy group, an amine fluorenylamino group, an aliphatic oxycarbonylamino group, an aliphatic sulfonyl group, an arylsulfonyl group or a quinone imine group, wherein the above hydrazine is Cu, and the above is called hydrazine, the above Cm is 0, and the above cn is 1 aspect. 34 200914995 Specific examples of the dye (dye) represented by the above formula (Ι), (Ι-1), and (Ι-2) (exemplified compounds C-1 to C-35, C-41 to C-) 59). However, the present invention is not limited to this.

Illustrative compound Μ 1 or 4, 5 or 8, 9 or 12 and 13 or 16 substituents (other 4 is H) Other 8 substituents C-1 Cu - S" \ &quot; My N (CH2CH2O C2H5) 2 Η C-2 Cu ~S\ /KCN(CIi2CH2〇CH3h Η C-3 Cu -shG^§och3 Η C-4 Cu /—\ CH3 -SH^j&gt;--CNCH2CH2OCH3 Η C-5 Cu /=\ 9Hi ~S &quot;Λ /)-C〇CHCH2OCH3 Η C-6 Cu —^-CNCH2CH2OCHs Η C-7 Cu -S-{~^-CN(C2H5)2 \-/ Q Η C-8 Cu -SH^ gN(CH3)? Η 35 200914995

Illustrative compounds Μ 1 or 4, 5 or 8, 9 or 12 and 13 or 16 substituents (other 4 is Η) Other 8 substituents C-9 Cu ~S^ ch3 cochch2och3 6 Η C-10 Cu - s^Q,n(ch2ch2oc2b5&gt;2 0 Η C-11 Cu—OCH2CH2OC2Hs Η C-12 Cu —S-SO2CH2CH2OC2H5 are CH3 groups at 2 or 3, 6 or 7, 10 or 11 and 14 or 15, respectively, and the remaining 4 Η C-13 Cu CH(CH2CH, OC3H5)? 6 Η C-14 Cu ~s^C) CN{CH2CH2OC2H5h 0 Η C-15 Cu r=\ —S&quot;-^^OCOCH2CH2〇C2H, respectively Or CH3 base on 3, 6 or 7, 10 or 11 and 14 or 15, and the remaining 4 are Η 36 200914995

Illustrative compounds Μ 1 or 4, 5 or 8, 9 or 12 and 13 or 16 substituents (other 4 are H) Other 8 substituents C-16 Cu -5; -^^)-ΝΜΟΝ{ΟΗ2αΐ2Ο02Η5) 2 Η C-17 Cu —S-&lt;^^)-KHC0(!:HCH20CH3 Η C-18 Cu /=\ ?H3 93⁄4 —S-^ ^-NCOCHCH2OCH3 ch/ Η C-19 Cu ch/ Η C- 20 Cu f V Ή 1 (〇2H5)2 Η C-21 Cu 1—S—^ NSOjCHg Η C-22 Cu Η 37 200914995

Exemplary compounds Μ 1 or 4, 5 or 8, 9 or 12 and 13 or 16 substituents (other 4 are H) Other 8 substituents C-23 Cu -s^o^s〇^cycH3 Η C- 24 Cu —S-&lt;^^&gt;-£〇2^(CH3CH2OCH3); Η C-25 Cu SOsNa ~S&quot;H^^-〇CH2CHi〇C3l I; Η C-26 V=0 —S~^ ^i-CN(CH2CH; OC2H5)2 Η C-27 Co CNCH3CH; OCH3 Η C-28 Co -s-^^-cncch3)2 Η C-29 Zn —S—{^^-NHC〇0HCH2〇CH5 Η C-30 v=o ~s^O 〇rH?(CF2)3CF〇H Η 38 200914995 S .3

ID exemplifies the substituent of the compound M 1 or 4, 5 or 8, 9 or 12 and 13 or 16 (the other 4 is H) The other 8 substituents C-31 Cu C1 0CH2CH20CHjCH20CH3 Η C-32 Cu ch3 OCH2CI-32 〇a I2CfI2OCH3 Η C-33 Cu -s-〇-^XC4li9 0 Η C-34 Cu Η C-35 Cu -SH^&gt;-pOC2H4OC2H4OCH3 Η 39 200914995

r exemplified by the substituent of the compound M 2 or 3, 6 or 7, 10 or 11 and 14 or 15 (the other 4 is H), the other 8 substituents C-41 Cu -S - ζ &gt; -CN (CH2CH2OC2H &lt; ) 2 Η C-42 Cu -S-^^C〇0HCH2〇CH3 Η C-43 Cu -sf~y~c^cu5)2 '~~&lt; q Η C-44 Cu _S^ CH3 COCHCH2〇CH3 6 Η C-45 Co CN(CH2CH2〇C2H5)2 6 Η 40 200914995 ? a

f id exemplifies the substituent of the compound M 2 or 3, 6 or 7, 10 or 11 and 14 or 15 (the other 4 is Η) The other 8 substituents C-46 Zn / - Λ 9 - S - CNCH2CH2OCH3 Η C-47 v=o ~s_&lt;G)-§ocH3 Η C-48 Cu _s_^}^ir0CH3 V_f Q is CH3 based on 1 or 4, 5 or 8, 9 or 12 and 13 or 16 respectively, and the remaining 4 It is Η C-49 Cu /=\ 9H3 ~~S \v ^NHCO chch2och5 Η 41 050 200914995

42 200914995

V

C-54

0«ΟΝ(〇2Κ,〇〇2Η5)2

0-CN(C2H5)2 C-58

0=C0CHg The coloring agent content in the total solid content of the colored photosensitive composition of the present invention is 50% by weight or more and 80% by weight or less, and it is preferred from the viewpoint of improving the absorbance and film hardenability by using a coloring agent. It is 52 wt% to 75 wt%, and particularly preferably 55 wt% to 70 wt ° / 〇. 43 200914995 (B) Thermal polymerization inhibitors are also described as point compound polymerization inhibitors. The coloring sensitivity of the present invention is as follows: For the content of the total solid content, it is necessary to include a thermal polymerization inhibitor having a large amount of money equal to or less than 10·3 Wt°-phenolic compound. Examples of the phenolic compound to be added as a thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, and di-t-butyl-p-cres〇l. Pyrogallol (pyr〇gall〇1), catechol, tributyl phthalate, 4,4'-thiobis(3-methyl-6-second butyl (4,4'_thio bis(3-methyl-6-t-butyl phenol) ), 2,2'-indenylene bis(4_mercapto-6-t-butylphenol) (2,2' -methylene bis(4_methyl-6-t-butyl phenol), 2,2'-arylene di(4-ethyl-6-tert-butylphenol), 4,4'-butylene double (6 - the third butyl group is expected) and the like. Among them, the thermal polymerization inhibitor represented by the following formula (7) is most preferable in terms of both sensitivity and stability over time.

OH

R1 General formula (7) In the formula (7), Ri represents a hydroxyl group or an alkoxy group, and R2 represents an argon atom 44 200914995 or an alkyl group. R] is preferably a hydroxyl group, a methyl group, a thiol group, a methoxy group, and most preferably a methyl group, a propyl group, and more preferably a hydrogen atom, a methyl group, a t group, or a butyl group. 7 base, the best is that the hydrogen atom is a gas atom to methoxy ii: t is a good example of which can be enumerated: hydroquinone, the total solids of the product = added amount of the paste of the present invention is equal to 1.0x10- 3 wt% denier is greater than or equal to 1·0χ10·5 wt% and less than qualitative is not sufficient. In addition, when ❿10·5 wt%, the use of low exposure amount over time will result in an increase of more than 1. The thermal polymerization inhibitor of the cap compound

Wt% and less than the material 5GxlG_4 force 1 is greater than 4 at 3.0X10 (10) and less than or equal to 3Gxl°G.4: the addition amount is greater than or equal to (c) resin grease. Preferably, the resin containing a predetermined amount of ΑS (S (hereinafter also referred to as a binder is obtained;; good self-heat resistance, developability, bismuth binder is preferably a linear organic polymer) The polymer 'moves to the organic di-II. The liquid-developable adhesive. The linear shape of the lemon has a t-knife compound having a polymer having a side bond, for example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Application No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The mercaptoacrylic acid copolymer, the acrylic copolymer, the itaconic acid copolymer, the crotonic acid copolymer, the maleic acid copolymer, and the partial ester described in the publication specification It is also useful to synthesize a maleic acid copolymer or the like, and similarly, an acid cellulose derivative having a diacidic acid in a side chain. In addition, an acid needle is added to a polymer having a hydroxyl group. Or a polyhydroxystyrene resin, Polypyrene (p〇iysiloxane) K 曰 'K (曱) 丙 2- (ethyl acetate) (p〇ly (2~hydroxy ethyl (meth)acrylate)) Polypyrorolidone or polyethylene oxide, polyvinyl alcohol (p〇ly Vinyi alcohol) and the like are also useful. Further, 'hydrophilic monomers can also be copolymerized, and examples thereof include: (fluorenyl)acrylic acid alkoxycarbazide, (meth)acrylic acid sulfonic acid vinegar, (mercapto) glyceryl acrylate (glycerol (meth)acrylate ), (meth)acrylic acid amine, N-methyl acrylamide, secondary and tertiary alkyl acrylamide, dialkyl (decyl) acrylate Aminoalkyl ester, morpholine (meth)acrylate, N-ethylene 0 piroxicam, N-vinylcaprolactam, vinyl milidine Vinyl imidazole), vinyl tris, (decyl) decyl acrylate, ethyl (meth) acrylate, branched or linear propyl (decyl) acrylate, branched or linear butyl (decyl) acrylate , (fluorenyl) phenoxy hydroxypropyl acrylate, and the like. 46 200914995 In addition to this, as a hydrophilic monomer, it contains a tetraglycosyl group (_hydr〇fUrf_), phosphoric acid, phosphoric acid vinegar, four grades of money (amm〇ni_ salt, ethyleneoxy chain, propylene A monomer such as a oxy group, a carboxylic acid or a salt thereof, or a morphylethyl group is also useful. The wax of the present invention is preferably a resin containing an unsaturated group. The resin contains an unsaturated group. Improves light sensitivity.

Examples of the resin containing an unsaturated group include the following resins as representative resins: a resin containing a plurality of groups and a glycidyl group-containing unsaturated compound such as glycidyl (meth)acrylate or propyl glycidyl ether or a resin obtained by reacting an unsaturated alcohol such as allyl alcohol, acrylic acid 2, or methyl propyl ether 2__ to react a carboxyl group-containing resin having a hydroxyl group with an unsaturated compound containing a free isocyanine group and an unsaturated acid anhydride. a resin obtained by reacting an addition reaction of an epoxy resin with an unsaturated carboxylic acid with a polybasic acid anhydride to form an addition of a conjugated diene copolymer and an unsaturated dicarboxylic anhydride. a resin obtained by reacting a reactant with a hydroxyl group-containing polymerizable monomer; a dehydration reaction is generated by an alkaline treatment to synthesize a resin having a specific functional group imparting an unsaturated group, and then the resin is subjected to an alkaline treatment to form A resin having an unsaturated group or the like. Among them, a resin obtained by reacting a carboxyl group-containing resin with a glycidyl group-containing unsaturated compound such as glycidyl methacrylate or allyl glycidyl ether; a resin obtained by polymerizing a resin obtained by polymerizing an acrylate-based compound with a (meth) acrylate having a free isocyanate group such as (nonyl)acrylic acid 2-isocyanate ethyl ester; ) to (3) a resin; a basic treatment to produce a de-47 200914995 reaction to synthesize a resin having a specific functional group imparting an unsaturated group' and then experimentally treating the above resin to form an unsaturated group Resin, etc. The resin in the composition of the present invention is particularly preferably one having at least one selected from the structural unit (the second structural unit) represented by any one of the following general formulae (1) to (3) as the unsaturated group. A polymer compound having a double bond moiety.

G—X—( II 〇 II〇 R5 C=C R4 R6 Formula (1) 11

II 〇C—八3—RI YC — C R10 R12 General formula (2) r16 1 r19 1 ~C~ I :c R17 R18 R20. _ In the above general formulae (1) to (3), A1, A2 and A3 Independently 48 200914995, respectively, a non-oxygen atom, a sulfur atom or _N(R21)-'R21 represents a hydrogen atom or a substituent group which may have a substituent. G1, G2 and G3 each independently represent a divalent organic group. X and Z each independently represent an oxygen atom, a sparing atom or _N(R22)_, and 22 R represents a hydrogen atom or an alkyl group which may have a substituent. γ represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent or _N(R23)_, and R23 represents a hydrogen atom or an alkyl group which may have a substituent. 1^ to R2〇 each independently represent an i-valent substituent. In the above formula (1), β to R3 each independently represent a monovalent substituent group, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among them, R1 and R2 are preferably a hydrogen atom, and R3 is preferably a hydrogen atom or a fluorenyl group. R4 to R6 each independently represent a monovalent substituent, and R4 may, for example, be a hydrogen atom or an alkyl group which may have a substituent. Among them, preferred are a hydrogen atom, a decyl group and an ethyl group. Further, R5 and R6 each independently include a hydrogen atom, a halogen atom, an alkoxy group, a repeat group, an exact group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a more substituted alkoxy group, a more substituted aryloxy group, a more optionally substituted alkylsulfonyl group, a more substituted aryl aryl group, etc., of which hydrogen is preferred. An atom, an alkoxycarbonyl group, an alkyl group which may have a more substituent, and an aryl group which may have a more substituent. Here, examples of the substituent which may be contained include a fluorenyloxycarbonyl group, an ethoxylated group, an isopropoxy group, a methyl group, an ethyl group, a phenyl group and the like. Α1 represents an oxygen atom, a sulfur atom or -N(R21)-, and X represents an oxygen atom, a sulfur atom or -N(R22)-. Here, R21 and R22 may, for example, be a hydrogen atom or an alkyl group which may have a substituent. 49 200914995 Machine base ® ' is preferably sub = with a substituent. = is an alkyl group which may have a substituent, a ring number, a carbon number, an aromatic group which may have a substituent, etc., wherein the carbon number is 2 〇 2 可 2 可, = number is b,. The direct-bonded or branched-like sub-sintering base, the number of two-competent ring-wei group having a substituent, the carbon number of 6 to 12, which can have a base group, (four) degree, developability In terms of heterogeneity, the substituents other than f may be better than the green: and the substituents of the hetero atom bonded by the alcohol group (for example, an amine group, a sulfur group (-), a carboxyl group, etc.). Substituents. A1 The structure represented by the formula (1) is as follows: #原^sulfur atom or na 21&gt;, χ is an oxygen atom, a sulfur atom or a hydrogen atom; and a sub-set 2 = a base 'R1, R2 are respectively Hydrogen methine, R is a hydrogen atom or a pyridyl group, r5, r6; 蜀 is a wind atom, an alkoxy group, an alkyl group or an aryl group, and r21 and R are each an alkyl group. Obtained, 'r7j*r9 independently represents the monovalent substitution,: the sub-substrate, and the substituent of the valerene of the genus 77, which has a hydrazine: a hydrogen atom, a south atom, and a second wire. Amino group, nitro group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which has a substituent, a silk group which may have a substituent, may further 50 200914995 A substituent having a substituent An oxy group, an alkylsulfonyl group which may have a more substituent, an arylsulfonyl group which may have a more substituent, etc., among which a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent are preferred. An aryl group which may have a more substituent. The substituent which may be present here may be similarly exemplified as the substituents exemplified in the formula (1). A2 represents an oxygen atom, a sulfur atom or -N(R21)-. Here, R21 may, for example, be a hydrogen atom or an alkyl group which may have a substituent. G2 represents a divalent organic group, and preferably an alkylene group which may have a substituent. Preferably, an alkylene group having a carbon number of 丨~, such as a substituent, a cycloalkylene group having a carbon number of 3 to 20, and a substituent having a carbon number of 6 to 20 may be mentioned. An aromatic group or the like, wherein a linear or branched alkylene group having a carbon number of 1 to 1 Å having a substituent, a cycloalkylene group having a carbon number of 3 to ί, and a carbon having a substituent The aromatic fused group having a substituent of 6 to 12 is preferable in terms of properties such as strength and developability.

Here, the substituent of G2 may preferably be a substituent other than a hydroxyl group and a substituent having a hetero atom bonded to a hydrogen atom (e.g., an amine group, a thiol group, a slow group or the like). =G2 has a hetero atom having a ruthenium of a ruthenium group, and the storage stability is lowered by the use of a ruthenium (〇niUm) salt compound as a starting point to be described later. Im, a sulfur atom, R23)- or an subunit which may have a substituent. Here, examples of R include a hydrogen atom, a burnt group which may have a substituent, and the like. 51 200914995

The structural unit represented by the formula (2) of R1 is preferably as follows: a sulphate '7Rll8, Rl2 is a hydrogen atom, a methoxy group is an oxygen atom, a sulfur atom or a na', and G2 is a substitutable a straight or branched-shaped Wei group having a carbon number of 1 to 1 G, a ring-formed ring-formyl group having a carbon number of 3 to 10, or a substituent having a carbon number of 6 to 12 and having a substituent The group 'Y is an oxygen atom, a sulfur atom, a ruler 23) or a phenylene group which may have a substituent, and R21 and r23 are each a hydrogen atom or an alkyl group which may have a substituent. In the above formula (3), R13 to Ri5 each independently represent a =3 generation of a working price, and examples thereof include a hydrogen atom and an alkyl group which may have a more substituent. Among them, R and Ri6 are each preferably a hydrogen atom. R15 is preferably a hydrogen atom or a fluorenyl group.

R to R2G each independently represent a monovalent substituent, and r16 to r2〇 may, for example, be a hydrogen atom; I atom, dialkylamino group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a more substituent, alkoxy group which may have a more substituent a aryloxy group which may have a more substituent, an alkyl group which may have a more substituent group; a 5-xanthene group, an arylsulfonyl group which may have a more substituent, etc., among which a hydrogen atom, an alkoxycarbonyl group, An alkyl group which may have a substituent, an aryl group which may have a more substituent. The substituent which can be introduced can be exemplified by the substituents exemplified in the formula (1). A3 represents an oxygen atom, a sulfur atom or _n(R21)_, and z represents an oxygen atom, a sulfur atom or _N(R22)-. R21 and R22 may be the same as those in the formula (i). G3 represents a divalent organic group, preferably a sub-52 which may have a substituent. 200914995 A pyridyl group is preferably an alkylene group having a carbon number of 丨~2〇 which may have a substituent, and a carbon number of 3 a cycloalkylene group having a substituent of -20, an aromatic group having a carbon number of 6 20 and the like, wherein the number of turns having a substituent of 1 to 1 〇 is linear or branched. The alkyl group, the cycloalkylene group having a substituent of 3 to 1 Å, and the aromatic group having a substituent having a carbon number of ό12 can be preferably selected in terms of properties such as strength and properties. . Here, examples of the substituent of G3 include a substituent other than a hydroxyl group and a substituent having a hetero atom bonded to a hydrogen atom (e.g., an amine group, a thiol group, a carboxyl group, etc.). In the above formula, the structural unit represented by the formula (3) is preferably as follows: R 2 r 4 is an argon atom, R 15 is a hydrogen atom or a methyl group, and R 16 to r 2 are a hydrogen atom or an alkoxycarbonyl group. An alkyl group having a substituent or an aryl group which may have a substituent, and A3 is an oxygen atom, a sulfur atom or _N(R21}_, Z is an oxygen atom, a sulfur atom or a -N(R22)-, R2], r22 a linear or branched alkylene group having a carbon number of 1 to 1 G which may have a substituent, a cycloalkylene group having a carbon number of 3 to 10 or a carbon number of An aromatic group of a substituent of 6 to 12, which is a structural unit represented by any one of the general formulae (1) to (3), which is formed by the above-mentioned "a structural unit containing an unsaturated double bond. The synthesis of the polymer compound can be carried out according to a known method, for example, the synthesis of the composition described in paragraphs [〇〇27] to [〇〇57] of JP-A-2003-262958. Further, (4) is carried out in the synthesis method 1) in the above publication. The above "polymer compound having an unsaturated double bond" is preferably a resin obtained by the synthesis method of the following [1] or [2]. [1] A polymer synthesized by using a compound represented by the following formula (5) as a copolymerization component, and removing a proton (pn)t〇n) to obtain L, thereby obtaining A method of obtaining a desired polymer compound of the structural unit represented by the above formula (1). R3

R4 R5 formula (5)

X-C-&gt;C~C-L 0 ^ ^ In the above formula (5), L represents an anionic leaving group, and preferably a halogen atom, an alkyl group or an arylsulfonyloxy group. R3 to r6, Al, G1 and X have the same meanings as in the above formula (1). Any of an inorganic compound or an organic compound can be used as the base for causing the detachment reaction. And the details of the "Finance Law" and the age record

The paragraphs of Japanese Patent Laid-Open No. 2G() No. 3-262958 are numbered [〇〇28] to [0033]. Preferred examples of the inorganic compound base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, and carbonic acid potassium. The organic compound base may be exemplified by sodium methoxide (n^ethoxideh). a gold oxide such as a shaft or a potassium tributoxide, an organic amine compound such as triethylamine, 0-bite or triisopropylethylamine, etc. [2] For the compound represented by the following formula (4) A polymer synthesized by copolymerization, a specific functional group is produced by an inertial treatment. 54 200914995 3 The method of removing X to obtain a radical reactive group: R29 R31 〇1ό=&lt; , / R24 R26 \ R30 ^a^g^Vc-cch 0 \ δ # 0 i

j General formula (4) towel, A4 represents an oxygen atom, a sulfur atom or a naphthalene 27), A represents a non-oxygen atom, a sulfur atom or _Nr28_, r24, respectively, independently representing hydrogen or an organic group of an valence, and χΐ represents utilization of detachment The group removed by the reaction, g4 represents an organic bonding group. η represents an integer of 1 to 1 。. ^(4) 中中中, Α4 is preferably an oxygen atom, and α5 is a better rolling atom. Further, R is preferably a methyl group, R25, R26, R29 and r3 are preferably a hydrogen atom, and R31 is preferably a fluorenyl group or a hydrogen atom. Further, χ1 ^ is preferably a bromine atom, and G4 is preferably an ethylene group. The details and preferred aspects of the above method are described in detail in Japanese Patent Laid-Open Publication No. 2003-335814. The polymer compound described in the above-mentioned [2] synthesis method is specifically a polymer compound described in JP-A-2003-335814, specifically, for example, (i) a polyethylene-based polymer compound, Ii) a polyurethane polymer compound, (iii) a polyurea polymer compound, and (iv) a poly(amine phthalate-urea) system 55 200914995 polymer compound, ( V) a polyester-based polymer compound, (vi) a polyamine-based polymer compound, (vii) an acetal-modified polyvinyl alcohol-based polymer compound, and each of these polymers are obtained. Specific compound. Specific examples of the compound represented by the above formula (5) include the following compounds (M-1) to (M-12), but the present invention is not limited to these compounds. 56

200914995

(M-4)

Ο 57 200914995

ο ,ci

HNOCT (Μ-9) ΌΙ Α (

HNOCT ΌΙ

/\^OTs ο (Μ-12) ΌΙ Ο 58 200914995 The compound represented by the above formula (6) includes the following compounds (i-1 ((i-52)), but the present invention is not limited to these compounds.

Η :H3 i-3

C02〆 0 ch3

M -Br O CH3 ch3 -Br =\ CH, -Br 0 CH3 O CH3 i-6 i-5

CH3 ch5 C〇2'-{CH2)6—〇~^—^Br C02-(CH2CH2&lt;^r^- o ch3 o ch3

Br i-8 ch3

I-7 ch3 -Br C02-(CH2CH2C%^-]-Br C02~(CH2CH20^- 0 CH3 0 CHg i-9 CH3 -Br i-10

CH, O CH3 C〇2-(CH2CHO)2-f- -Br CH3 O ch3 i-11 H2 CH, ^ Vr,3 ===( Q^3 C02—(CHg^HO)^--^~I —Br C02^(CHg^HO^C~—Br CH3 O CH3 CH3 O ch3 59 200914995 H3

CH3 co2—ch2ch2〇2G—(ch2)4—o- -Br 0 CHa 14 CH, C02—CH2CH2〇2C~(CH2)5—o-c- -Br 0 CHa f i-15_ CH3 O CH3 M6

I-17

B〇r^^°~9_?H_CH3 b〇r^^c^&lt;p-cpH-CH; i-18 M9

O

〇2^Y 〇-Cji~CH-CH3 0 Br 〇 Br i-20

I-21

,〇2^ΤΓ〇η3 c〇2-(CH2CH2%^ Bu 22

I-23 CH3

C02~(CHaCHO)rC-j-Br C02 — (CH2CH2C%^-fH-CH3 CHg 0 CH3 0 Br 60 -25200914995 i-24 CH, C02-(CH2CH0)t-^ i~26 -27 i-2fi • Br

CHf oh3 o ch3 C02-(CH2CH0)4-a C02-CH2CH202C—(CH2)4—oc- -Br CH〇〇CH3 CH3 -Br O CH3 CH, C〇2~~CH2CH2O2C (CHaJs~~0—C- I-29

Br 〇 CHg CH.

Kc〇r^°~? i-30

I-32

p2C- -Br

H ch3 -Br ο ch3 0 CH3 i-31

H oh3 -Br

O CH ΛϊΟΝΗ eight v〇2°&quot; CHg -Br CH,

CH 3 Br CON. CH3 ch3 i-33

CH, -Br CO 丫^〇2. Ten Hope OH CH3 CH, 61 200914995

62 200914995 i-42

, C02/\^〇HH-CH3 O O 0=S II 〇 ~^VcHs i-43 i-44 CH: ch3 C〇2&quot;*--CH2&quot;· i-45 i-46

0〇2 ΌΗ2--&quot;〇2 C_ CH, -Br ch3 , co2, ych3 9h3 02C- -Br

CH 3 H o ch3 -Br CH, i-47 ch3 o2cch3 ch3 3 -Br co2-^Y^ci 〇2〇 3 H3C--Br ch3 63 -49 200914995 i-48

Ch3 ( CH3 COf^〆0 一?, Bu Ci 2 〇 CH3 i-50 C -C — 0 Cu co^r ch3 〇 °'9~h〇'S-CH3 o ch3 o i-51

^〇r-^〇-cn|-cH 3 9H3 N (C2H5)3 Br- -52 O CH3 , from the viewpoint of performing developmental development, the lipid preferably has a color selected from CGQH, qing, ρ〇 At least one acid group of 3Η2, (10)^. Further, the acid value of the resin in the present invention is 5 mg K 〇 H / g 〜 7 〇 (10) g, more preferably W mg KOH / g ~ 60 mg K 〇 H / g of Fan Mail / g ~ 50 mg K0H / g The scope. If === === the material has a tendency to peel off the pattern. Further, if the acid value is gK0H/g, the developability is lowered. ,,, σ structure 70. Ting is effective in terms of residue suppression and rectangular pattern formation in the fine pattern of 64 200914995.

丨人〇'Rb, cooh In the above formula (4), Ra represents a hydrogen atom group, and RB represents a divalent bond group. The alkane having a snail of 1 to 6 is preferably a hydrogen atom or a methyl group. The above RB is a divalent bonding group which may be a substituted sub-alkyl group of 1 and 2, and is represented by a carbon number.

And v respectively represent a single bond or a carbon number as a ring, U represents a substituted cyclohexyl ring, a benzophthalene ring, or a slave; (where ' Rd and ~ respectively represent the carbon number independently Is a sub-filament of ^—=, a substituted benzene ring or a naphthalene ring, = taken,; = heart, wherein the number of inputs is one = the content of the acid value is, for example, based on the acid group in the resin molecule. Further, by averaging the monomers containing the acid groups constituting the resin, a resin having a desired acid value can be obtained. From the viewpoint of developing the residue in the unexposed portion, the above-described aspect of the present invention Resin tweezers are resins in which agglomerated components are contained in Yoshiki. ^Inhibition of pattern collapse due to overheating in post-baking (p〇st bake)' Resins which may be included in the composition of the present invention It is preferable that the following structure 65 200914995 具有 has the second structure _ 1.5 times 戍 1 5 ratio (mole ratio) represented by the general formula (4) and has the above-described formula (1) to the jth represented by the middle The structural unit is hardly expressed by the above formula (1) to the ratio of the second '〇 times or more represented by the above formula (4) to 3), the first structural unit, preferably has a 3.G times or above = (four) chemical properties and reduces the development of residual (four) views into the tree can be included in the 练 molecular towel to The range of m^^ in the range of ^2 to (3) includes at least one selected from the first structural unit represented by the above formula (1), and the step i is greater than or equal to 37 m〇1% and less than or equal to 9〇_, Ϊ方二f is equal to 4〇Μ• and less than or equal to circumference, and, in terms of hardenability, it is preferable that the range of i is equal to 40 _% and less than or equal to 85 m_ The resin of the structural unit represented by the formula (1) is the resin of the structural unit which is represented by the formula (1), and the weight average molecular weight of the resin in the composition is preferably 30° to 300,000. 'Better is 4〇, _~_ of 5〇, 〇〇〇~·, _, especially good is 5_〇~·, _ is good for the shore = the weight average molecular weight of the resin, for example, gel can be used涞^The chromatograph (GdPermeati〇nChr〇mat〇g, Gpc) is measured in terms of both the suppression of pattern peeling and the suppression of development residuals. The content of the component, the content of the resin 66 200914995 == is 0.01 wt% to 2 G wt%, more preferably i wt% to i〇 wt%, further preferably 3 wt% to 7 wt%. (D) Polymerizable compound It is preferred that the present invention is a polymerizable compound (polymerizable single. The polymerizable monomer preferably has a ratio of equal to or greater than that under normal house. [m'' and at least one can be carried out. A compound obtained by addition polymerization of an ethylenically unsaturated group. (4) A scale of a polymerizable monomer: polyethylene glycol (poly(ethylene) acrylate), polypropylene glycol = (mercapto) acrylic acid S-, (fluorenyl) acrylic acid phenoxyacetic acid and other monofunctional propionate or methyl acrylate vinegar; polyethylene glycol di (meth) acrylate vinegar, three, methyl bromide three ( Methyl) acrylic acid vinegar, neopentyl glycerol eopentylglycoi di (meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (Methyl propylene coffee, dipentaerythritol penta (meth) acrylate vinegar, dipentaerythritol hexa (meth) acrylate, hexane diol (mercapto) acrylate Ester, trihydroxypyridyl propane: (propylene propylene oxypropyl, tris(oxy oxyethyl) uric acid vinegar, : = three methyl ethyl ethane fresh epoxy epoxide epoxy secret addition to the official Erqi, re-implementation of (meth)acrylic acid vinegar (methyl) propylene vinegar, jilite a day mouth 48·4 Π〇 8 5 tiger, Japanese patent special public Zhao 5〇 _6 〇 34, = Patent _ 51·37193 Fresh sulphuric acid peak carboxylic acid vinegar, Japanese Patent Special Open Detective 48 Detective No. 83, Japanese Patent Special ZHAO = _43191, Japanese Patent Special Public Show No. 52 In the bulletin, the poly(4) dilute acid lanthanum, epoxy resin and (mercapto)acrylic acid anti-67 200914995 should be the product of epoxy acrylates such as polyfunctional acrylate or mercaptopropyl vinegar and these (methyl a mixture of acrylates. Further, Japanese Patent Publication No. Vol. 20, No. 7 on pages 300 to 308 of Japan is described as a polymerizable monomer for photohardening twins and oligomers. In addition to the above polymerizable monomer, a carboxyl group-containing radical polymerizable monomer of the following formula (III-1) or (ΙΠ·2) can be suitably used. Further, in the formulae (ΙΙΙ-1) and (ΠΙ_2), when τ or G is an oxyalkylene group, the terminal on the carbon atom side is bonded to R, X and W. R/TV ^ ch2^g}w ch2—(g^w n nX (lll-1) w*ch“f called two z_cH2_fch2_^w «

2_t # CH"G}pW CI^-fG^W R: H2C=C-C-〇-

x: —nr〇H, both H: —CH, a 1〇CH _ z: -o- 2 , ~~〇CH2CH2- -〇CH2CH2CH2- -〇CH2CH2CH2CH2-

Li /λ. . \ N o o 〇ch2ch2 -OCH2CH2CH2 - one OC Hj CH2CH2CN2

-〇〇V G; —ch2 _^ In the general formula (ΙΠ-1), n is 〇~14, and m is. ^ II-2) where '~ is the same as the general formula (m-1), R&lt;x, 3, or 3 or more = 2 = 3 can be respectively C = 3 =; =:示基基性性单68 (1) 200914995 h2c=ch c=o

I o ch2 II ο

It 〇

H2C=CH-C-〇-CH2—C-CH2-O-C-CH2-CH2-C-OH 0 ch2 &quot; ’ ό ό=ο h2c=ch

CMO - H c II c 2 H 〇 2C 2 I Hll H - H = H CICIOICICICIOICIC -I T= 2CH2-2C hchh H2

CMO i H2 CH i H2 c I CMO 〇 I _2 o 2-c2 o Η -I Η ~ H = H clclolclclc[olclc II i = ch2c 2 H 2 H c H

H (2) H c-- c H2 〇2C 2 o H = H - H -- H CICIOICICICIOICIC II I= 2CH2-C2 hchh h2c -2 _2 c n2 〇2 2 I Η _ Η I Η I CICIO Icicle 10 —c ho

Yuo H2 5 I H2 c i cno H2 -c H2 c

H -0 CMO

H (3) 69 (4)200914995 h2c= =CH 1 〇1' c=o C -CH2 - CH2 — q_OH ό ό o ch2 CH2 H2C=CH-C-0 -CH2- -c-ch2- -0 - Ch2 -c -ch2-oc -ch2 -c 6 ch2 ch2 0 0 1 0 c=o 1 C-CH2_CH2—C-〇H h2c= =CH li J1 0 0 II ο h2c= rCH C=0 I o h2c: Two CH C=0 I o CH2 CHo i

H〇一C一HaC—h^C—C—O—CH2—C—CH2〇—CH2~C—CHg—0—C—CH2 _CH2 —OH (5) r, O ΓΙo I)o ch2 ό 0 =0 H2C=CH h2c=ch 0=0 i 0 ?H2 ch2 0 c=o H2c 2 0H h2c=chc=o 1o ch2 IIo HO-C-HjC^H^CC~〇—CH2· II IIo o C— CH2 —0~*CHj-C _CH2 ~~〇-C -CH2 _CH2 0 -OH (6) h2c:

Ch2 0c=o ^CH ch2 6 c—ch2-ch2

-C-OH 70 200914995 CH3 hoC-Cc=o Io ch2 ch3 H2C—C ~C—O—CH2—C—CH2—O—C—CH2 _CH2 C-OH 〇CH2 〇0 c=o h2c=c ch3 ch3 Ch3 h2c=c h2c=c 0=0 c=〇? 0 9H3 ch2 ch2 1 H2C—C —C—Ο—CH2 —C—CH2 一〇一CHp — c _c 0 ch2 ch2 〇1 0 1 c^oc= o h2c=c 1 h2c=c ch3 ch3 ch3 CH3 h2c=c H2〇=C c=o 1 c=o 1 1 〇0 9H3 CH2 J ch2 1 *- II 〇ch2 I 〇c=o ch2 0 II 〇〇 u) -CH, -C-OH II 〇(8) H2C=C—C—O—CH2 —ό—CH2—0~CH2—C _CH2 _O-C—CH2-CH2 _C—OH (9) h2c=c ch3 C —CH2-CH2—C-OH 〇〇71 (10) 200914995 4' CH3 H2C—Q—C~0* CHZ Η2〇=9 6_ch2-ch2-〇-〇h9 0 ch2 .cH2^c-ch2-o- ch2-c-cH2-〇-c-ch2-ch2-c-〇h ch2 ° 0 C^OI o ch2 1 0 0 0=0 c-ch2h HaC— ch3 6 ch3 CH$ Η2〇=0 Η2〇=ό c=oc=〇1 1 0 0 ch2 ch2 Q—O-CH2~~C-CHj —^ 0 ch2 ch2 ό 0 c=o 6-0 H2C=C h2c=c ch3 ch3 CH3 ch3 h2c=c h2c=c 6 2 0 c:oooo ch2 γ· «2 ν-/Π2 II o (11) (12)

HO-C-HaC-HaC-c-o-CHs-C-c^-O-C^-c-CHa-O-C-CHa-CHa-c-OH. . 9H2 ch2 δ c=o h2c=c CH,

C—~-CH2~CH2-C-OH

II o o The content of the polymerizable monomer in the coloring photosensitive composition is preferably from 1 Gwt% to 45 wtm ^ wt% to 4 G wt%, particularly preferably from 15 wt% to 35 Å. If the range is within the above range, the sufficient degree of hardening and the degree of hardening of the exposed portion can be sufficiently maintained in the unexposed portion, and the unexposed enthalpy/mixing property can be prevented from being remarkably lowered. (E) Photopolymerization initiator 72 200914995 A preferred type of dyed photosensitive composition of the present invention. The photopolymerization initiator is selected from the viewpoints of having a polymerization monomer ratio, an absorption wavelength, availability, cost, and the like. Start. Compound (hal〇methyl^^ aryl-substituted coumarin-Pak), compound: U_nedime〇, benzophenone (_乡h_e) compound^y acetophenone compound and its derivative Iron complexes and salts thereof, lanthanide compounds and the like.衣 埤 埤 - 本 _ 喔 喔 喔 活性 活性 活性 活性 活性 活性 活性 活性 卤 卤 卤 卤 卤 卤 卤 卤 卤 卤 卤 卤 卤 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性The photopolymerization initiator can be called the vinyl group methyl-homo-azineated group described in the publication No. 59.1281. The product is disclosed in Japanese Patent Laid-Open No. 53-133428, "Sentence 1 and Base" - 4,6_Double ((4) ) _ s-triazine compound bis = yl)-2,6-bis(dimethyl)-s-triazine compound. Decamine is basically one, one, another fluorenyl-(3,4-dimethylene dioxetyl 1 hydrazine, 3,5-triazine, 2,6-bis(trichloromethyl) o-methoxy Phenylphenyl 73 200914995 Triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butane bake)-average two ° Qin, 2 -Trichlorodecyl-4-amino-6-p-nonyloxyphenidinyl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-all Triazine, 2-(4-methoxy-qin-1-yl)-4,6-bis(dichloroindenyl)-homo-di- Qin, 2-(4-ethoxy-na-l-yl -4,6-bis(trichloroindenyl)-s-triazine, 2-(4-butoxy-naphthalen-1-yl)-4,6-bis(trichloroindenyl)-homotriosine ,2-[4-(2-decyloxyethyl)-heptan-1-yl]-4,6-bis(triseodecyl)-s-triazine, 2-[4-(2-ethoxyl) Ethyl)-naphthalen-1-yl]-4,6-bis(trichloroindenyl)-s-triazine, 2-[4-(2-butoxyethyl)-phenol-1-yl]-4 ,6-bis(trimethylsulfonyl)-s-triazine, 2-(2-decyloxy-naphthalen-1-yl)-4,6-bis(trichloroindenyl)-s-triazine, 2-( 6-decyloxy-5-mercapto-naphthalen-2-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(6-decyloxy-naphthalen-2-yl)- 4,6-bis(trichloroindenyl)-s-triazine, 2-(5-decyloxy-naphthalen-1-yl)-4,6-bis(trichloroindenyl)-all three 2-(4,7-Dimethoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(6-ethoxy-naphthalen-2-yl -4,6-bis(trichloroindenyl)-s-triazine, 2-(4,5-dimethoxy-naphthalen-1-yl)-4,6-bis(trichloroindenyl)-s-triazine , 4-[p-oxime, Ν-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloroindenyl)-s-triazine, 4-[o-indenyl hydrazine, hydrazine -bis(ethoxycarbonylcarbenyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[p-oxime, fluorene-bis(chloroethyl)aminophenyl ]-2,6-bis(trichloroindenyl)-s-triazine, 4-[o-indenyl-p-fluorene, anthracene-bis(chloroethyl)aminophenyl]-2,6-bis(trichloro) Mercapto)-s-triazine, 4-(p-chloroethylaminophenyl)-2,6-bis(trichloroindenyl)-s-triazine, 4-(p-oxime-ethoxycarbonyl hydrazine Aminophenyl)-2,6-bis(trichloroindenyl)-s-triazine, 4-[p-oxime, fluorene-bis(phenyl)aminophenyl]-2,6-bis(trichloro Methyl)-s-triazine, 4-(p-chloro-chloroethylcarbonylaminophenyl)-2,6-bis(trichloroindenyl)-s-triazine, 4-[p-quinone-(p-oxygen) Phenyl) 74 200914995 benzylamino] phenyl] 2,6-bis(trichloroindenyl)-homo-di-D-Qin and 4-[inter-N,N-bis(ethoxymethyl)methyl) Phenyl]-2,6-double ( Trichloromethyl)-s-triazine, 4-[m-bromo-p-oxime, fluorenyl-bis(ethoxycarbonylindenyl)aminophenyl]-2,6-bis(trichloroindenyl)-all Oxazine, 4-[m-gas·p-, Ν-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloroindenyl)-s-triazine, 4-[m-fluoro- Ν, Ν-bis(ethoxycarbonylguanidino)aminophenyl]-2,6-bis(trichloroindenyl)-----------------[[[[[[[[[[ Aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-chloro-p-anthracene, fluorenyl-bis(ethoxycarbonylindenyl)amine Phenyl-2,6-bis(trichloromethyl)-s-triazine, 4-[o-fluoro-p-oxime, fluorenyl-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-double (trimethyl sulfhydryl)-s-triazine, 4-[o-di-p-, hydrazine-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-chloro-p-oxime, fluorene-bis(chloroethyl)aminophenyl]-2,6-bis(trichloroindenyl)-s-triazine, 4-[o-fluoro-p-quinone, hydrazine- Bis(chloroethyl)aminophenyl]_2,6-bis(trichloroindenyl)-s-triazine, 4-[m-di-p-quinone, anthracene-bis(chloroethyl)amino stupyl]_2 , 6-bis(trichloromethyl)-all three. Qin, 4_[Intermediate gas-to-purine, Ν-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[intermediation-opposite, Ν -bis(chloroethyl)aminophenyl]·2,6-bis(trichloroindenyl)-s-triazine, 4-(m-bromo-p-fluorenyl-ethoxycarbonyldecylaminophenyl)_2 ,6-bis(trichloromethyl:l·s-triazine, 4-(m-chloro-p-oxime-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloroindenyl)-all Triazine, 4-(m-fluoro-p-ethoxybenzylaminomethylphenyl)-2,6-bis(trichloroindenyl)-s-triazine, 4-(ortho-p-N-ethoxylate) Alkyl decylaminophenyl)-2,6-bis(triseodecyl)-homo-trimium, 4-(o-chloro-p-N-ethoxycarbonyldecylaminophenyl)·2,6 · bis (trichlorodecyl-s-triazine, 4-(o-fluoro-p-oxime-ethoxycarbonyldecylaminophenyl)_2,6-bis(trichloromethyl 75 200914995)-s-triazine, 4 -(m-bromo-p-chloroethylaminophenyl)-2,6-bis(trichloroindenyl)-s-triazine, 4-(m-gas-p-N-chloroethylaminophenyl) -2,6-bis(trichloroindenyl)-s-triazine, 4-(m-fluoro-p-N-gas ethylaminophenyl)-2,6-di(trichloroindenyl)-s-triazine , 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloroindenyl)-s-triazine, 4-( Chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-chloroethylaminophenyl)-2, 6-bis(trichloromethyl)-s-triazine, etc. In addition, it can also be used effectively: TAZ series manufactured by MIDORI Chemical Co., Ltd., TAL-107, TAZ-110, TAZ-104, TAZ-109, TAZ- 140, TAZ-204, TAZ-113, TAZ-123; T series manufactured by PANCHIM, T-OMS, T-BMP, TR, TB; Irgacure series and Darocure series manufactured by Ciba Specialty Chemicals , Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, Darocure 11734; 4'-bis(diethylamino)-dibenzophenone, 2-(0-benzoquinone (肟)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(0-ethylindenyl)-1-[9-ethyl_6-(2- -9 曱醯 ) ) ) ) ) ) ) ) ) ) ) ) -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 -9 2-phenylacetophenone, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer 2-(o-methoxyphenyl)-4,5-diphenylimidazolium , 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2 -(2,4-dimethoxyphenyl)-4,5-diphenylimidazolium dimer, 2-(p-nonylnonylphenyl)-4,5-diphenyl rice bran dimer , benzoin isopropylether, etc. 76 200914995 Among the above initiators, preferred are the lanthanoid compounds, and the most preferred ones are 2-(0-apo-methyl sulfhydryl) small [4-(phenylthio)phenyl]], 2-octanedione. ,^((^乙醯基肟)-1 _[9-ethyl-6-(2-methylphenylhydrazino)_9H-indazol-3-yl]ethanone. The best fat light above Commercially available products of the polymerizable initiators include CGI-124 and CGI-242 (the above are manufactured by Ciba Specialty Chemicals Co., Ltd.). In the composition of the present invention, other known photopolymerization initiators may be used. The photopolymerization initiator is specifically exemplified by the vicinal polyketolaldonyl compound disclosed in the specification of U.S. Patent No. 2,367,660, the α-carbonyl group disclosed in the specification of U.S. Patent Nos. 2,367,661 and 2,367,670. The compound, the acyloinether disclosed in the specification of U.S. Patent No. 2,448,828, the alpha-hydrocarbon-substituted aromatic alcohol ketone compound disclosed in the specification of U.S. Patent No. 2,722,512, and the specification of U.S. Patent Nos. 3,046,127 and 2,951,758. The disclosed polynuclear ruthenium compound, the triene disclosed in the specification of U.S. Patent No. 3,549,367 A combination of a benzyl imidazole dimer/p-aminophenyl ketone and a benzothiazole compound/trihalo-s-triazine compound disclosed in Japanese Patent Publication No. Sho 51-48516 Further, a sensitizer or a light stabilizer may be further used in combination with the photopolymerization initiator. Specific examples of the sensitizer or the light stabilizer include benzoin, benzoin, 9-fluorenone, and 2-Chloro-9-fluorenone, 2-mercapto-9-fluorenone, 9-anthrone, 2·bromo-9-fluorenone, 2-ethyl-9-fluorenone, 9, 10-蒽酉昆, 2-ethyl-9,10- onion 酉, 2_t-butyl-9,10-, '酉昆, 2,6- 77 200914995 dichloro-9,10·恩醌, oxalate (xanth()ne), 2_f-based oxo-poor, 2-methoxy oxy onion _, 2-methoxyxanthone, ^ (-brain-, 2,4-diethyl Thioxanthone, acridine _ (ca (1_) = basics, benzil, dibenzalacetone, p-(dimethylamino)phenylstyryl ketone, ί (Dimethylamino)phenyl-p-methylstyryl ketone, benzophenone, p-methylamino)benzophenone (or midrolone (Midiler) Sket〇ne)), for J diethylamino) benzophenone classes benzene, anthracene, benzene feed or Bing the 2nd 5_6 special eight Japanese publication described Bing thiazole compounds II:

TINUVIN 1130, TINUVIN 400, etc. S The amount of the above photopolymerization initiator to be used is relatively high relative to the total solid content, preferably from 1. G wt% to 4 G. G wt% 'better 岐 2 5 鸠 to g wt 〇 /. Especially good is 5·〇 wt%~· wt%. If the use of ruthenium by photopolymerization is less than l.G Wt%, it is difficult to carry out the polymerization, and if it exceeds _ wei, the polymerization rate is increased, but the molecular weight is lowered and the degree of material is weakened. The coloring photosensitive composition of the present invention preferably contains a solvent. When the topping agent satisfies the solubility and coating properties of the composition, it is preferable to apply the coating property and the safety, and it is particularly preferable to consider the solubility of the dye and the binder, ..., and the totality. The solvent used in the preparation of the composition of the present invention is preferably, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, methyl:di-:iso-amyl acetonate, isobutyl acetate, and lysine. Acidic and succinct, butyl succinate, succinate, oxyacetic acid, oxyacetate 78 200914995 butyl oxyacetate, methoxy methoxyacetate, ethyl methoxyacetate, A Butyl oxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, decyl 3-methoxypropionate, 3- Ethyl methoxypropionate, decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, decyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxyl Propyl propionate, methyl 2-methoxypropionate, ethyl 2-nonoxypropionate, propyl 2-methoxypropionate, decyl 2-ethoxypropionate, 2-ethoxyl Ethyl propionate, methyl 2-methoxy-2-mercaptopropionate, ethyl 2-oxo-2-mercaptopropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate, methyl pyruvate, ethyl acetonate, pyruvate, ethyl acetate A, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.; ethers, such as diethylene glycol dioxime ether, tetrahydrofuran, ethylene glycol monoterpene ether, Ethylene glycol monoethyl ether, methyl cellosolve acetate (ethylene glycol monoterpene ether acetate), ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate), two Ethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol methyl ether Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones I, such as mercaptoethyl, cyclohexanone, 2-heptanone (2-heptanone), 3-heptanone, etc.; aromatic hydrocarbons such as toluene, diphenylbenzene, and the like. Among these solvents, more preferred are decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl 79 200914995 ether. , butyl acetate, 3, methoxy propionate, 2, heptanone, cyclohexanide, ethyl carbitol acetate (diethylene glycol monoethyl acetate acetate), T Kikabi alcohol B (diethylene glycol alone acetic acid vinegar), propylene glycol methyl ether, propylene glycol oxime ether acetate and the like. (G) Other additives in the composition of the present invention may be blended into various additives as needed, such as a filler, a polymer compound other than the above, a surfactant, a densely-promoted, an antioxidant, and a substance. Bu Ning fresh sputum preparations, etc. Specific examples of the additives include fillers such as glass and alumina; and other binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyacrylic acid fluoroalkyl ester. Polymer compound; surfactant such as nonionic, cationic or anionic; [alkenyl dimethoxydecane, vinyl triethoxydecane] vinyl tris(2-methoxyethoxy) Decane, N-(2-aminoethyl)_3_aminopropylmethyldimethoxyoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxy decane, 3_ Aminopropyl triethoxy decane, 3-glycidoxy propyl trioxane oxime C calcination, 3-glycidoxypropyl decyl dimethoxy decane, 2-(3,4_i oxy group Cyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxysulfonium, 3-chloropropyldimethoxycarbazide, 3-methylpropenyloxypropyltrimethoxylate An adhesion promoter such as decane or 3-mercaptopropyltrimethoxydecane; an antioxidant such as thiobis(4-mercapto-6-tert-butylphenol) or 2,6-di-t-butylphenol; -(3-tert-butyl-5-mercapto-2-hydroxybenzene UV absorbers such as _5_chlorobenzotriazole or alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate 0 200914995 —χ Further, in order to promote the solubility of the unexposed part, further improve the present In the case of the developability of the composition of the invention, it is preferable to add an organic retinoic acid to the composition of the present invention, which is preferably a low molecular weight organic carboxylic acid having a molecular weight of 1,000 or less. Specific examples thereof include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylie acid. Such as aliphatic monosinic acid; oxalic acid (〇xalic acid), malonic acid, succinic acid, glutaric acid, adipic acid, giga Pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid , dimercaptomalonic acid, mercapto succinic acid, tetradecyl succinic acid, citraconic acid, etc.; aliphatic diteric acid; 1,2,3-propane tricarboxylic acid (tricarballylic) Acid), aconitic acid, fatty acid such as camphoric acid; benzoic acid, toluic acid, cumic acid, 3,4-dimethyl An aromatic monocarboxylic acid such as hemellitic acid or 3,5-dimethylbenzoic acid; phthalic acid (p Hthalic acid ), isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, 1,2,3,5-benzenetetracarboxylic acid ( Mellophanic acid ), aromatic polycarboxylic acid such as pyromellitic acid; phenylacetic acid, hydratropic acid, hydrocinnamic add, mandelic acid, benzene Other toxic acids such as butyl succinic acid, atr〇pic acid, cinnamic acid, cinnamylidene acetic acid, coumaric acid (coumaric 81 200914995 acid), umbellic acid, and the like. <Color filter and method for producing the same> The color filter of the present invention is formed by using the above-described colored photosensitive composition of the present invention. Specifically, the colored photosensitive composition of the present invention is applied onto a support by a coating method such as spin coating, cast coating, or roll coating to form a colored photosensitive composition layer. Then, the coloring level composition layer formed on the support is exposed through a predetermined mask pattern, and then developed with a developer. Thereby, a colored pattern is formed on the support, whereby a color filter can be manufactured. Further, the method of manufacturing the color filter of the present invention may include a step of hardening the above-described photoresist pattern by heating and/or exposure, as needed. The radiation used at this time is particularly preferably an ultraviolet ray such as g-ray, h-ray or i-ray. Examples of the support include sodium glass for use in a liquid crystal display device, bronosilicate glass (Pyrex (R) glass, etc.), quartz glass, and a transparent conductive film attached to the glass. The body, or a photoelectric conversion element substrate used in a photographic element or the like, for example, a germanium substrate or the like, or a complementary metal oxide semiconductor (CMOS) or the like. These supports also have the form of a black stripe that separates the individual elements. Further, in the above-mentioned support, it is also possible to provide an undercoat for improving the adhesion to the upper layer, preventing the substance from diffusing or flattening the surface of the substrate, and the above-described method of manufacturing the color filter of the present invention. The developing solution to be used may be any one which can dissolve the composition of the present invention and does not dissolve the composition of the radiation irradiating portion 82 200914995. Specifically, a combination or an aqueous solution of various organic solvents can be used. The organic solvent may, for example, be the above-mentioned solvent used in the preparation of the composition of the present invention. The alkaline aqueous solution can be used, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, hydrogen. Tetraethylammonium oxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4.0]·7-deca-ene', etc., at a concentration of 0.001 wt% An alkaline aqueous solution obtained by dissolving in an amount of from 0.01% by weight to about 1% by weight. Further, when a developer containing the above alkaline aqueous solution is used, it is usually washed with water after development. Further, the color filter of the present invention can be suitably used for a solid-state image pickup device such as a CCD, and is particularly suitably used in a high-resolution CCD element or CMOS element of more than 5 million bismuth. The color filter of the present invention can be used, for example, as a color chopper disposed between a light receiving portion of each element constituting the CCD and an I microlens for collecting light. [Examples] Hereinafter, the present invention will be specifically described by the examples, but the present invention is not limited to the following examples unless otherwise stated. Furthermore, "parts" are weight basis unless otherwise stated. (Example 1) 1) Preparation of primer solution A photoresist solution was prepared by mixing and dissolving the following materials: 83 200914995 • Propylene glycol monomethyl ether acetate... 19.20 parts (PGMEA) • Ethyl lactate... 36.67 parts•Resin...30.51 parts [40% PGMEA solution of benzyl methacrylate/methacrylic acid/-2-hydroxyethyl methacrylate copolymer (Morby = 60: 22: 18) Dipentaerythritol hexaacrylate ... 12.20 parts (photopolymerizable compound)

V • Polymerization inhibitor (p-oxyl) ...... 0.0061 parts. Fluorine-based surfactant... 0.83 parts (F-475, manufactured by Otsuka Ink Chemical Industry Co., Ltd.) • Photopolymerization initiator...0.586 parts (TAZ-107 (trihalomethyltriazine photopolymerization initiator), manufactured by mid〇rj Chemical Co., Ltd.). 2) Wafer substrate (support) with undercoating The 6 inch wafer was placed in an oven and heat treated at 2 °c &gt; c for 30 minutes. Then, the above-mentioned first resist liquid is applied onto the Shi Xi wafer to dry the film thickness, and the oven towel is heated and dried for 1 hour to form an undercoat layer to obtain an undercoat layer.矽 Wafer substrate. 3) Preparation of coloring photosensitive composition (composition of the present invention) Compound of soil tree is mixed and dissolved 'Preparation: color sensitivity = Further, diquaternary tetradecyl hexanoic acid vinegar is refined using a column Founder. 84 200914995 &lt;Composition A-l&gt; ......8 ......份......8.16 parts...3.84 parts...5.38 parts•Cyclohexanone•Colorant A [Illustrative Compound C-58 as described] • Colorant B [Example compound a below]. Dipentaerythritol hexaacrylate • • 1.50 ^ Photopolymerization initiator CGI-242 (1-(0-ethyl brewing) -i-[9-ethyl 曱美苯甲甲基)-Sister·Ten Sit I base] 嗣 嗣, manufactured by Ciba Specialty Chemicals Co., Ltd., hiring ^ starting ship. Resin (exemplified compound A below) .. 〇 49. Dicyclohexyl decylamine '丄2...0.61 parts. Surfactant (Manufactured by Dainippon Ink Co., Ltd. 0.02 parts of p-methoxyl (thermal polymerization inhibitor) 0.1% cyclohexa , liquid solution ^, ... 0.028 parts 4) Forced time-lapse of coloring photosensitive composition (age)

The forced menstrual test was carried out by allowing the colored salty resin composition A-1 prepared in the above 3) to stand in a box at 40 ° C for 7 days. ~ 5) Coating, exposure, and smearing of the coloring photosensitive composition ^ The composition obtained by coating the above 4) on the undercoat layer of the primer-coated ray substrate obtained in the above 2) The material forms a photocurable coating film. Further, a 12-inch heat treatment (prebake) was performed using a hot plate of a loot:, and the dried film of the coating film was 0.5 μm. Then, an i-ray stepper is used to expose the FPA-3_i5+ (manufactured by Canon) to a wavelength of 365 nm: 85 200914995 by an island pattern mask having a pattern of 1.2 μm square. The exposure amount was changed in the range of 〇mJ/cm to 2500 mJ/cm, and the exposure amount was changed in units of 5 〇mJ/cm 2 . Thereafter, the tantalum wafer substrate on which the irradiated coating film was formed was placed on a horizontal rotating platform (sable) of a Spin Shower developing machine (dw-30 type; manufactured by Chemitronics), using CD-2000 ( Fuji Film Electronics Materials (manufactured by Fuji Film Electronics Materials Co., Ltd.) performs a 60-second secondary development (pU (jdie development) at 23 C to form a colored pattern on the tantalum wafer substrate. The coloring is formed by a vacuum chuck (chuck) method. The patterned silicon wafer substrate is fixed to the horizontal rotating platform, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotating device, and is supplied in a shower form by a nozzle from a rotation center above the rotation center. Rinse treatment with water' followed by spray drying to obtain an axe filter. 邑 邑 6) Evaluation of pattern adhesion after development

Observe and confirm the _ &amp; obtained by the above using an optical microscope at 100 times, and confirm that all the patterns are intimate and residual! Ancient 3 / τ / 2, the minimum exposure of two no eggs: (mJ / cm). 7) Evaluation of developability of unexposed portion The development of the unexposed portion was evaluated by using a scanning electron microscope (SEM), and the developed pattern was observed in (8), and evaluated according to the following evaluation criteria. σ - Evaluation criteria - ◎: The unexposed portion can be completely removed. 86 200914995 ?.:f, slightly remnant, but within the allowable range. There are many disabilities that cannot be allowed. And (Examples 2 to 10, Comparative Example: ~4) 0 cases, 1 _ 'Use the color sword, the tree wax, and the respective inhibitors in the composition Ai, and the addition amount (content) The coloring agent formed by the coloring agent and the resin shown in the enamel == the product, ~ Α · 13 ' instead of the coloring photosensitive composition (four) seven mMS, in the same manner as in the first embodiment, the color 嘑 is made to cry and develop The minimum exposure required for the post-pattern adhesion = color, rf and cut to the tree. Further, ii is carried out 3 _ and _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Unexposed portion developable colorant A colorant B content structure content type content Example 1 A-1 exemplified compound C-58 a 60% A 2.4% p-methoxyphenol 0.00014% 200 ◎ Example 2 A-2 exemplified compound C-54 a 60% A 2.4% p-ethoxyphenol 0.00091% 300 ◎ Example 3 A-3 exemplified compound C-45 a 60% A 2.4% p-ethoxyphenol 0.00002% 100 ◎ Example 4 A-4 Exemplary compound C-30 a 60% A 2.4% catechol 0.00015% 300 〇 Example 5 A-5 B c 60% A 2.4% 2,2'-arylene di(4-ethyl-6- Tributyl expectate) 0.00015% 400 〇 Example 6 A-6 B c 60% B 2.4% hydroquinone 0.00015% 450 〇 Example 7 A7 CI Acid Red 57 c 60% C 2.4% Hydroquinone 0.00012% 500 〇Example 8 A-8 CI Acid Blue 249 a 60% A 2.4% Hydroquinone 0.00015% 200 ◎ Real A-9 CI Acid a 60% B 2.4% Hydroquinone 0.00015% 200 〇88 200914995 Example 9 Sex Blue 249 Example 10 A-10 CI Pigment Green 7 CI Pigment Yellow 83 60% A 2.4% p-Oxime Phenol 0.00014% 200 〇 Comparative Example 1 A-11 CI Acid Blue 249 a 60 % A 2.4% p-methoxyphenol 0.00110% 600 ◎ Comparative Example 2 A-12 CI Acid Blue 249 a 60% A 2.4% p-Oxime Phenol 0.000009% 100 X Comparative Example 3 A-13 CI Acid Blue 249 a 60 % A 2.4% N-nitrosophenylhydroxylamine aluminum salt 0.00014% 800 ◎ Comparative Example 4 A-14 CI Acid Blue 249 a 60% A 2.4% TEMPO 0.00014% 1000 ◎ 89 200914995

a 90 200914995

b

91 200914995

Catechol OH 0r0H

P-ethoxyphenol OH OMe 2,2'·•-indenyl bis(4-ethyl-6-tert-butylphenol)

92 200914995 Hydroquinone

OH

OH N-nitrosophenylhydroxylamine aluminum salt

(Examples 11 to 12, Comparative Examples 5 to 6) In Example 1, in accordance with the description of Table 2, coloring photosensitive compositions A-14 to A-17 having the following compositions were used instead of coloring sensitivity. A color filter was produced and evaluated in the same manner as in Example 1 except for the composition A-1. The results are shown in Table 2. <Composition A-14> • Cyclohexanone... 80 parts • Colorant A [CI Acid Blue 249] ... 6.80 parts • Colorant B [Illustrative Compound a] 3.20 parts • Dipentaerythritol hexaacrylate 7.38 • Photopolymerization initiator... 1.50 parts 93 200914995 CGI-242 (1-(0-acetoxy)-l-[9-ethyl-6-(2-methylphenylhydrazine) )-9H-carbazol-3-yl]ethanone, manufactured by Ciba Specialty Chemicals Co., Ltd., oxime-based initiator) • Resin (exemplary compound A) ...... 0.49 parts • Dicyclohexyl decylamine... 0.61 parts • Interface Active agent (F-781 manufactured by Dainippon Ink Co., Ltd.) 0.02 parts • 0.1% cyclohexanone solution of p-nonoxylphenol (thermal polymerization inhibitor)...0.028 parts f

<Composition A-15> • Cyclohexanone... 80 parts • Colorant A [CI Acid Blue 249] ... 10.88 parts • Colorant B [Example compound a] ...... 5.12 parts. Dipentaerythritol Hexyl acrylate 2.38 parts. Photopolymerization initiator 0.50 parts CGI-242 (1-(0-ethylindenyl)-1-[9-ethyl-6-(2-mercaptophenyl)- 9H- Oxazol-3-yl]ethanone, manufactured by Ciba Specialty Chemicals Co., Ltd., lanthanide initiator) Resin (exemplified compound A) 0.49 parts. Dicyclohexyl decylamine... 0.61 part. Surfactant (Daichi Ink) F-781 manufactured by Co., Ltd. ... 0.02 parts • 0.1% cyclohexanone solution of p-methoxyphenol (thermal polymerization inhibitor)...0.028 parts &lt;composition A-16&gt • Cyclohexanone... 80 parts 94 200914995 • Colorant A [CI Acid Blue 249] . &quot;...6.12 parts • Colorant B [Example compound a] below.. • 2.88 parts. Pentaerythritol hexaacrylate.., 8.38 parts • Photopolymerization initiator. ..... 1.50 parts CGI-242 (1-(0-ethenyl)-1-[9-ethyl-6-(2 -Methylbenzhydryl)_9H-carbazol-3-yl]ethanone, manufactured by Ciba Specialty Chemicals, lanthanide initiator) • Resin (exemplified Compound A) ....0.49 parts • Cyclohexyl decylamine. ..... 0.61 parts. Surfactant (F-781 manufactured by Dainippon Ink Co., Ltd.) ....0.02 parts • p-Oxime 0.1% cyclohexanone solution (thermal polymerization inhibitor)....0.028 parts &lt;composition A-17&gt; •cyclohexanone.....80 parts•colorant A[CI Acid Blue 249]. ..... 11.22 parts • Colorant B [The following exemplified compound a] .. 5.5.2 parts. Dipentaerythritol hexaacrylate.. 1.1.8 parts • Photopolymerization initiator. ..... 0.50 parts CGI-242 (1-(0-ethenyl)-1-[9-ethyl-6-(2-mercaptobenzoic acid)-9H-indazol-3-yl]ethanone, vapor Made by Bajing Chemical Co., Ltd., 肟-based initiator) • Resin (exemplary compound A) .. .., 0.49 parts. Dicyclohexylmethylamine. ..... 0.61 part • Surfactant (Daily Ink) F-781 manufactured by Co., Ltd. ...... 0.02 parts 95 200914995 [Table 2] Coloring photosensitive composition Colorant resin Thermal polymerization inhibitor Adhesion minimum exposure [mJ/cm2] Unexposed portion development Sex coloring agent A coloring agent B content structure content content implementation Example 11 A-14 CI Acid Blue 249 a 50% A 2.4% p-Methoxyphenol 0.00014% 100 〇 Example 12 A-15 CI Acid Blue 249 a 80% A 2.4% P-methoxyphenol 0.00014% 500 ◎ Compare Example 5 A-16 CI Acid Blue 249 a 45% A 2.4% p-Methoxyphenol 0.00014% 100 X Comparative Example 6 A-17 CI Acid Blue 249 a 82.5% A 2.4% P-methoxyphenol 0.00014% 800 ◎ % 96 200914995 According to the colored patterns formed in Tables 1 and 9, that is, the coloring photosensitive composition of the invention can be used for Is, and it can be displayed in the low exposure period after the exposure to the phoenix or the temperature. Low. The good name is steep and the unexposed portion is also developable. Although the present invention has been disclosed in the preferred embodiment as above, the invention is defined as 'any 菽 菽 , , , ” ” ” ” ” 〜 乂 乂 乂 乂YES = = =: The spirit of the invention is as follows: Patent application: = Protection of the invention [Simple description of the diagram] None. [Main component symbol description] None 0 97

Claims (1)

200914995 X. Patent application scope: 1. A colored photosensitive composition for a solid-state photographic element, characterized in that the coloring photosensitive composition has a weight ratio of 5 G or more and less than or equal to 5 parts by weight relative to the total solid content. (9) a color percentage of the color, and a freshness inhibitor of the compound of (4) which is greater than or equal to 1 Gxl () _ 5 weight percent and less than or equal to 1.0% by weight. 2. The coloring y-component for photographic elements according to the first aspect of the invention, wherein the coloring agent is dyed in an organic solvent, as in the solid-state photography described in claim 1 The element is colored and double-bonded, and comprises a resin selected from the group consisting of the following structural unit groups (1) to (3), wherein any one of the formulas is selected from m/group to >' a structural unit and an acid group, and having a molar ratio in the second structural unit group represented by the constitutive list and a molar ratio of the first structural unit to the upper and the tearing is 15 times or more than General formula (1) 98 200914995 1 2 R1IC—R1 110 OIR I I 2 G type no 9 ο 1 2 RIC1R 1118 cfR 6 | 7 τ— I if Ric—R i z I 3 G 式通-&quot;Γ\ο COOH General formula (4, /, medium 'in the above formula (1) to (3), VIII, VIII and VIII; showing oxygen atom, sulfur atom or tan 21)_ , r21 represents a hydrogen base ^ St base of the burnt group; "2 and G3 respectively represent 2 points of the illusion of the silk material "sulfurogen ^ 2" R table can not have a substituent alkyl; Y represents the oxygen number is now ' , a phenylene group which may have a substituent or -N(R23)-, R23矣1, a gas 8 or a group which may have a substituent; r1, r2, r3, r4, r5, ^^ R^Ri〇 'RU ' Rl2' Rl3' Rl4' Rl5' Rl6' Rl?' ^, independently represents a monovalent substituent; further, the above formula (A represents a gas atom or a carbon number of 1 to 6), 2 / [Jia 99 200914995 Bonding group. 4. The photographic element according to Item 1 of the patent application uses a multi-photosensitive composition in which the weight average molecular weight of the above resin is 30,000 or more and 300,000 or less. 5, 5. The susceptibility of the mil photographic element according to the first aspect of the patent application, which further comprises a starting agent. 6. The photographic element for solid-state photographic element according to claim 1 Sex composition Wherein the photopolymerization initiator is further contained in an amount of 1.0 wt% to 40.0 wt%, based on the total solid content. 7. A method for producing a color filter for a solid-state photographic element, comprising: The step of applying a colored photosensitive composition for a solid-state image sensor according to any one of the first to sixth aspects of the present invention to a support to form a colored photosensitive composition layer; and the coloring sensitivity by the photomask a step of forming a pattern on the support by exposing and developing the composition layer. A color filter for a solid-state photographic element, which is used in any one of items 1 to 6 as claimed in the application. The solid-state photographic element is formed by the use of a photosensitive composition. 100 200914995 VII. Designation of the representative figure: (1) The representative figure of the case is: No. (2) The symbol of the symbol of the representative figure is simple: None. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: None.