JP2010085604A - Photosensitive resin composition, method for manufacturing color filter and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having high sensitivity, allowing formation of a high-definition pattern following a design dimension and suppressing generation of scum on pixels, and to provide a color filter formed from the photosensitive resin composition and a method for manufacturing the color filter. <P>SOLUTION: The photosensitive resin composition contains at least a dye, a compound expressed by general formula (I) or general formula (II), and a photopolymerization initiator. The color filter formed from the photosensitive resin composition and the method for manufacturing the color filter are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a method for producing a color filter, and a color filter.

The color filter is an essential component for a liquid crystal display.
Since the liquid crystal display is energy saving and compact as compared with the CRT as a display device and is equivalent or better in performance, it is replacing the CRT as a television screen, a personal computer screen, and other display devices. In recent years, the development trend of liquid crystal displays is moving from conventional monitor applications where the screen has a relatively small area to TV applications where a large screen and high image quality are required.

Liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor applications. That is, improvement in contrast and color purity is required. In order to improve contrast, a curable composition for producing a color filter is required to have a finer particle size of a colorant (organic pigment or the like) to be used.
Further, in order to improve color purity, a higher content of the colorant (organic pigment) in the solid content of the curable composition for producing a color filter is required.

On the other hand, in the color filter for a solid-state image sensor, further higher definition is desired. Therefore, a technique using an organic solvent-soluble dye instead of a pigment as a colorant has been proposed (for example, see Patent Document 1).
In addition, for color filters for solid-state imaging devices, there is a demand for thin color patterns, and in order to make thin films with the same color density as before, the use of colorants in curable compositions for color filter production It is required to increase the content rate.

  As a conventional method for forming a high-definition pixel pattern, a photosensitive resin composition mainly composed of an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator, and a colorant is used. A photosensitive resin composition containing a mixture of erythritol hexaacrylate and dipentaerythritol pentaacrylate has been proposed (see, for example, Patent Documents 1 to 3).

  Moreover, sensitivity is improved by containing 0.01 to 20% by weight of a thiophosphite compound in a photosensitive resin composition mainly composed of an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, and a colorant. A method for producing a practical resin composition by improving and shortening the exposure time has been proposed (for example, see Patent Document 4).

  As a method for producing a sharp pattern at the pixel pattern edge portion, which has better developability, an acrylic copolymer having a carboxy group and an ethylenically unsaturated group in the side chain is used as a binder component, and a coloring component is added thereto. A photosensitive resin composition containing a polyfunctional thiol compound and a photopolymerization initiator has been proposed (see, for example, Patent Document 5).

  Furthermore, the photosensitive resin composition containing the monofunctional monomer which has an imidazole ring in a molecule | numerator in the photosensitive resin composition which has an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a coloring agent as a main component is provided. It has been proposed (see, for example, Patent Document 6).

JP-A-7-140656 JP-A-10-104412 JP 2000-81508 A JP-A-5-255419 Japanese Patent Laid-Open No. 5-281734 JP 2001-21713 A

In a curable composition to which a conventional pigment dispersion system is applied, there are problems such as color unevenness because the pigment is relatively coarse particles, and it is difficult to further improve the resolution. Thus, it was not suitable for applications requiring a fine pattern.
Further, in both cases for liquid crystal displays and solid-state imaging devices, the curable composition for producing a color filter contains a colorant, and thus light that is a necessary component for curing the curable composition. The content of the polymerization initiator and the photopolymerizable monomer is limited, the strength is insufficient, and the curability is insufficient and the adhesion to the hard surface as the base material cannot be sufficiently obtained. However, there is a problem that the adhesion strength of the pixel pattern is reduced by development, and the pixel pattern is peeled off from the substrate after the pixel pattern is formed. Furthermore, there is a problem that scum (floating) occurs on the obtained pixel pattern, and it is difficult to manufacture a highly accurate pixel pattern. Therefore, even when forming a fine pixel pattern, it is a negative photosensitive resin that has high precision and excellent adhesion strength with the substrate, and forms a high-definition pixel pattern without generating scum on the pixel. Development of a composition has been desired.
Moreover, in the photosensitive resin composition in the invention described in the said patent documents 1-6, it was difficult to form a high-definition pixel pattern.

  The present invention has been made in view of the above problems. An object of the present invention is to provide a photosensitive resin composition that is highly sensitive, can form a high-definition pattern as designed, and can suppress the occurrence of scum (floating) on a pixel. It is.

The above-described problems of the present invention have been solved by the following means <1>, <6>, and <7>. It is described below together with <2> to <5> which are preferred embodiments.
<1> a photosensitive resin composition comprising at least a dye, a compound represented by the following general formula (I) or the following general formula (II), and a photopolymerization initiator;

（式（Ｉ）中、Ｒ¹¹及びＲ¹²は各々独立に水素原子又はメチル基を表し、Ｒ¹³は置換基Ｐ１又は末端が置換基Ｐ１で置換されたアルコキシ基を表し、Ｒ¹⁴及びＲ¹⁵は各々独立に水素原子又は無置換のアルキル基を表し、Ｒ¹⁶は、水素原子、２−クロロエチル基、メトキシエトキシエチル基又は無置換のアルキル基を表し、ｎは０又は１を表す。）

(In the formula (I), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, R ¹³ represents a substituent P 1 or an alkoxy group whose terminal is substituted with the substituent P 1, R ¹⁴ and R ¹⁵ Each independently represents a hydrogen atom or an unsubstituted alkyl group, R ¹⁶ represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group or an unsubstituted alkyl group, and n represents 0 or 1.)

（式（ＩＩ）中、Ｒ²¹及びＲ²²は各々独立に水素原子又はメチル基を表し、Ｒ²³は末端が置換基Ｐ２で置換されたアルコキシ基を表し、Ｒ²⁴及びＲ²⁵は各々独立に水素原子又は無置換のアルキル基を表し、Ｒ²⁶は、水素原子、２−クロロエチル基、メトキシエトキシエチル基又は無置換のアルキル基を表す。）

(In the formula (II), R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, R ²³ represents an alkoxy group substituted at the end with a substituent P 2, and R ²⁴ and R ²⁵ each independently And represents a hydrogen atom or an unsubstituted alkyl group, and R ²⁶ represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group, or an unsubstituted alkyl group.

<2> The total content of the compound represented by the general formula (I) and the compound represented by the general formula (II) is 0.01 to 10% by weight with respect to the total solid content of the photosensitive resin composition. % Of the photosensitive resin composition according to <1>,
<3> The photosensitive resin composition according to <1> or <2>, wherein the photopolymerization initiator is an oxime initiator,
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the photopolymerization initiator is an oxime ester initiator.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the dye is a dye exhibiting a color selected from the group consisting of red, green, and blue.
<6> The step of applying the photosensitive resin composition according to any one of <1> to <5>, and exposing the coating layer of the photosensitive resin composition formed by coating through a photomask. A process for producing a color filter including a process and a process of forming a pattern by developing,
<7> A color filter produced by the method for producing a color filter according to <6>.

  According to the present invention, there is provided a photosensitive resin composition that is highly sensitive, can form a high-definition pattern as designed, and can suppress the occurrence of scum (floating) on a pixel. I was able to.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention is characterized by containing at least a dye, a compound represented by the following general formula (I) or the following general formula (II), and a photopolymerization initiator.

（式（Ｉ）中、Ｒ¹¹及びＲ¹²は各々独立に水素原子又はメチル基を表し、Ｒ¹³は置換基Ｐ１又は末端が置換基Ｐ１で置換されたアルコキシ基を表し、Ｒ¹⁴及びＲ¹⁵は各々独立に水素原子又は無置換のアルキル基を表し、Ｒ¹⁶は、水素原子、２−クロロエチル基、メトキシエトキシエチル基又は無置換のアルキル基を表し、ｎは０又は１を表す。）

(In the formula (I), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, R ¹³ represents a substituent P 1 or an alkoxy group whose terminal is substituted with the substituent P 1, R ¹⁴ and R ¹⁵ Each independently represents a hydrogen atom or an unsubstituted alkyl group, R ¹⁶ represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group or an unsubstituted alkyl group, and n represents 0 or 1.)

（式（ＩＩ）中、Ｒ²¹及びＲ²²は各々独立に水素原子又はメチル基を表し、Ｒ²³は末端が置換基Ｐ２で置換されたアルコキシ基を表し、Ｒ²⁴及びＲ²⁵は各々独立に水素原子又は無置換のアルキル基を表し、Ｒ²⁶は、水素原子、２−クロロエチル基、メトキシエトキシエチル基又は無置換のアルキル基を表す。）

(In the formula (II), R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, R ²³ represents an alkoxy group substituted at the end with a substituent P 2, and R ²⁴ and R ²⁵ each independently And represents a hydrogen atom or an unsubstituted alkyl group, and R ²⁶ represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group, or an unsubstituted alkyl group.

The color of the photosensitive resin composition of the present invention may be any color as long as it is not black, but is preferably a color selected from the group consisting of red, green, and blue.
Moreover, it is preferable that the photosensitive resin composition of this invention contains a solvent.

The photosensitive resin composition of the present invention comprises a composition containing a dye using a polymerizable monomer having a specific structure, so that it has high sensitivity and excellent adhesion strength with a substrate, and has high definition as designed. A pattern can be formed and the occurrence of scum (floating) on the pixel can be suppressed.
Hereinafter, each component which comprises the photosensitive resin composition of this invention is explained in full detail.

[1] Dye The photosensitive resin composition of the present invention contains at least one dye. The dye can be used without any particular limitation, and can be selected from conventionally known dyes for color filters. Of the dyes, organic solvent-soluble dyes that are soluble in organic solvents are preferred.

  For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And dyes described in JP-A-6-194828.

  Chemical structures include pyrazole azo, anilino azo, aryl azo, pyrazolo triazole azo, pyridone azo, etc., triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolo. Dyes such as pyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used. Particularly preferred are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes and anthrapyridone dyes.

  Moreover, when developing with water or an alkali, an acidic dye and / or its derivative are suitable from a viewpoint of removing a binder and / or dye completely by development. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively. Hereinafter, the acidic dye and its derivative will be described.

~ Acid dyes and their derivatives ~~
The acid dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, and phenolic hydroxyl group, but is soluble in an organic solvent and a developing solution used during development processing, and forms a salt with a basic compound. It is selected in consideration of all required performances such as properties, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

Specific examples of acid dyes are given below. However, the present invention is not limited to these. 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 chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid 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, 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, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 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;

Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
Modern 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;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern 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;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3; and derivatives of these dyes.

Among the above acid dyes,
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, 74;
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;
A dye such as acid green 25; and derivatives of these dyes are preferred.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; I. Solvent Orange 45; Rhodamine B, Rhodamine 110, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5-[(phenylsulfonyl) amino] -2,7-naphthyl, etc. Acid dyes and derivatives of these dyes can also be preferably used.

  As the derivative of the acidic dye, an inorganic salt of an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, an amide compound such as a sulfonamide of an acidic dye, or the like may be used. There is no particular limitation as long as it can be dissolved when the photosensitive resin composition is prepared in a solution, and the solubility in the organic solvent described below and the developer used in the development process, the absorbance, and other components in the composition It is selected in consideration of all necessary performance such as interaction with components, light resistance, heat resistance and the like.

The “salt of an acid dye and a nitrogen-containing compound” will be described. The method of forming a salt of an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.
Nitrogen-containing compounds that form salts with acid dyes, and nitrogen-containing compounds that form amide bonds with acid dyes are soluble in salt or amide compounds in organic solvents and developers, salt-forming properties, dye absorbance / color value, It is selected in consideration of all of the interaction with other components in the composition, heat resistance as a colorant, light resistance, and the like. When selecting only from the viewpoint of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, more preferably a molecular weight of 300 or less, more preferably a molecular weight of 280 or less, and a molecular weight of 250 or less. Particularly preferred.

  The molar ratio of nitrogen-containing compound / acid dye (hereinafter abbreviated as “n”) in “salt of acid dye and nitrogen-containing compound” will be described. n is a value that determines the molar ratio between the acidic dye molecule and the nitrogen-containing compound (amine compound) forming a counter ion, and can be freely selected according to the salt forming conditions of the acidic dye-amine compound. Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selecting from the standpoint of absorbance only, n is preferably a value between 0 <n ≦ 4.5, more preferably a value between 0 <n ≦ 4, and 0 <n. It is particularly preferable to take a numerical value between ≦ 3.5.

  Since the above acidic dye is an acidic dye due to the introduction of an acidic group in its structure, it can be converted to a non-acidic dye by changing its substituent. In other words, the acid dye may suitably act during alkali development, but on the other hand, it may be over-developed, and a non-acid dye may be preferably used. As the non-acidic dye, those having no acidic group of the above acidic dye can be suitably used.

Next, a compound preferable as a dye will be described.
~~ Compound represented by formula (M1) ~~
In the present invention, the dye preferably contains at least one azo dye represented by the following general formula (M1).

In the general formula (M1), Z ^M1 represents an electron withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Z ^M1 is preferably an electron withdrawing group having a σ _p value of 0.30 to 1.0. Preferred examples of the group include an electron-withdrawing substituent described later. Among them, an acyl group having 2 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, and 1 carbon atom. A C-12 alkylsulfonyl group, a C6-C18 arylsulfonyl group, a C1-C12 carbamoyl group, or a C1-C12 halogenated alkyl group is preferable. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms, and most preferred is a cyano group.

In the general formula (M1), B ¹ and B ² each independently represent —CR ^M1 ═, —CR ^M2 ═, or a nitrogen atom. Particularly preferably, B ¹ represents -CR ^M1 = and B ² represents -CR ^M2 =.

R ^M1 and R ^M2 are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group Substituted by hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group, aryl group or heterocyclic group Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, alkylsulfo Group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group with the proviso that each group may be further substituted.

Among the groups represented by R ^M1 or R ^M2 , preferred groups include a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a carboxy group, a carbamoyl group, and a cyano group. Each of these groups may further have a substituent.

In the general formula (M1), Z ^M2 has the same meaning as R ^M1 and R ^M2 , and preferred groups include a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and more preferably An aliphatic group or an aromatic group.

In the general formula (M1), R ^M5 and R ^M6 are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl. Represents a group, an arylsulfonyl group, or a sulfamoyl group, and each group may further have a substituent. Among the groups represented by R ^M5 or R ^M6 , preferred groups include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, and an arylsulfonyl group, and more preferably a hydrogen atom. An atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and most preferably a hydrogen atom, an aryl group, or a heterocyclic group. An embodiment in which each of these preferred groups further has a substituent is also suitable. However, R ^M5 and R ^M6 are not simultaneously hydrogen atoms.

R ^M1 and R ^M5 and / or R ^M5 and R ^M6 may be bonded to each other to form a 5-membered ring or a 6-membered ring.

In Formula (M1), R ^M3 and R ^M4 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl Represents a group, an arylsulfonyl group, or a sulfamoyl group. Among these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, and an arylsulfonyl group are preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable.

In the general formula (M1), Q ^M represents a monocyclic 5-membered heterocyclic group. This heterocyclic group may be substituted, may be a saturated ring, or may have an unsaturated bond. Preferable atoms constituting Q ^M include a nitrogen atom, an oxygen atom, a sulfur atom and a carbon atom. Specific examples of the 5-membered heterocyclic ring include, for example, 1,2,4-thiadiazole ring, 1,3,4-thiadiazole ring, 1,2,5-thiadiazole ring, furan ring, thiophene ring, pyrrole ring, and oxazole ring. , Isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, triazole ring, furazane ring, pyrroline ring, pyrrolidine ring, imidazoline ring, imidazolidine ring, pyrazoline ring, pyrazolidine ring, 1,2-oxathiolane ring, And 2H-tetrazole ring. However, the condensed ring is not included.

In the general formula (M1), Z ^M1 is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or an arylsulfonyl group having 6 to 18 carbon atoms (preferably a cyano group), and R ^M1 and R ^M2 are hydrogen An atom, an alkyl group, an alkoxycarbonyl group, a carboxy group, a carbamoyl group, or a cyano group, wherein Z ^M2 is a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group (preferably an aliphatic group, an aromatic group) ) comprising, R ^M5 and R ^M6 represents a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or arylsulfonyl group (preferably a hydrogen atom, an aryl group, a heterocyclic group), R ^M3 and R ^M4 are a hydrogen atom, aromatic group, heterocyclic group, acyl group, alkylsulfonyl group, arylsulfonyl group (preferably a hydrogen atom, aromatic group, heterocyclic group), and Q ^M is a monocycle 5 If a heterocyclic group are more preferable.

When the azo dye represented by the general formula (M1) is a water-soluble dye, an ionic hydrophilic substance is present at any of the positions of Q ^M , R ^M1 , R ^M2 , R ^M5 , and R ^M6 . It is preferable to further have a group. Examples of the ionic hydrophilic group include a sulfo group, a carboxy group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxy group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxy group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include an alkali metal ion (eg, sodium ion, potassium ion) and an organic cation (eg, tetramethylguanidinium ion). ) Is included.

Each group in the general formula (M1) may further have a substituent. When each of these groups further has a substituent, examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, a complex Ring group, cyano group, carboxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxy A carbonyloxy group, an aryloxycarbonyloxy group, a substituted amino group substituted with an alkyl group or an aryl group or a heterocyclic group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, Alkylsulfonylamino group, ant Rusulfonylamino group, aryloxycarbonylamino group, nitro group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, sulfamoyl group, sulfo group, or heterocyclic thio group, ionic Examples thereof include hydrophilic groups, and each group may be further substituted with these groups.
The azo dye represented by the general formula (M1) is obtained by bonding two or more azo dyes represented by the general formula (M1) via each group or the substituent in the general formula (M1). Is also included.

  Hereinafter, specific examples (example compounds ma-1 to ma-7, mb-1 to mb-7, mc-1 to mc-7, md-1) of the compound (azo dye) represented by the general formula (M1) ~ Md-7, me-1 to me-7, mf-1 to mf-7, and mx-1 to mx-4). However, the present invention is not limited to these.

  The synthesis of the compound (azo dye) represented by the general formula (M1) can be performed with reference to, for example, the methods described in paragraph numbers [0074] to [0077] of JP-A-2006-39301. .

~~ Compound represented by formula (Y1) ~~
Moreover, the compound represented by the following general formula (Y1) can be preferably used as a dye.

<< Definition of substituents >>
Here, the “substituent” in the compound represented by the general formula (Y1) and the compound represented by the following general formula (K1) will be described.
The “substituent” may be any group that can be substituted, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an alkyloxy group, an alkenyloxy group, Alkynyloxy group, aryloxy group, heterocyclic oxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group, alkynyloxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, alkylsulfonyl group, alkenylsulfonyl group, Alkynylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfonyloxy group, alkenylsulfonyloxy group, alkynylsulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, Rufamoyl group, alkylsulfonamide group, alkenylsulfonamide group, alkynylsulfonamide group, arylsulfonamide group, heterocyclic sulfonamido group, amino group, alkylamino group, alkenylamino group, alkynylamino group, arylamino group, heterocyclic ring Amino group, alkyloxycarbonylamino group, alkenyloxycarbonylamino group, alkynyloxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, alkylsulfinyl group, alkenylsulfinyl group, alkynylsulfinyl group, arylsulfinyl group, Alkylthio group, alkenylthio group, alkynylthio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxy group, alkyloxyamino , Alkenyloxyamino group, alkynyloxyamino group, aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialkyloxyphosphinyl group, dialkenyl Examples thereof include an oxyphosphinyl group, a dialkynyloxyphosphinyl group, and a diaryloxyphosphinyl group.

In the general formula (Y1) and the following general formula (K1), examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
In the general formula (Y1) and the following general formula (K1), the aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. . The aliphatic group may have a branch and may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl Group, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group, and allyl group.
In the general formula (Y1) and the following general formula (K1), the aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aromatic group preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms. Examples of the aromatic group include phenyl group, p-tolyl group, p-methoxyphenyl group, o-chlorophenyl and m- (3-sulfopropylamino) phenyl group.
In the general formula (Y1) and the following general formula (K1), the heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include aliphatic groups, halogen atoms, alkyl and arylsulfonyl groups, acyl groups, acylamino groups, sulfamoyl groups, carbamoyl groups, ionic hydrophilic groups and the like. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group and 2-furyl group.

In the general formula (Y1) and the following general formula (K1), the carbamoyl group includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.
In the above general formula (Y1) and the following general formula (K1), the alkoxycarbonyl group includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.
In the above general formula (Y1) and the following general formula (K1), the aryloxycarbonyl group includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 12 carbon atoms is preferable. Substituents include ionic hydrophilic groups. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
In the general formula (Y1) and the following general formula (K1), the acyl group includes an acyl group having a substituent and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.
In the general formula (Y1) and the following general formula (K1), the alkoxy group includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As an alkoxy group, a C1-C12 alkoxy group is preferable. Examples of the substituent include an alkoxy group, a hydroxy group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

In the above general formula (Y1) and the following general formula (K1), the aryloxy group includes an aryloxy group having a substituent and an unsubstituted aryloxy group. As the aryloxy group, an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.
In the above general formula (Y1) and the following general formula (K1), the acyloxy group includes an acyloxy group having a substituent and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
In the general formula (Y1) and the following general formula (K1), the carbamoyloxy group includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.
In the general formula (Y1) and the following general formula (K1), the heterocyclic oxy group may be unsubstituted or substituted, and the heterocyclic ring includes a furan ring, a thiophene ring, a pyrrole ring, and an oxazole. Ring, imidazole ring, pyrazole ring, furazane ring, pyridine ring, pyrimidine ring, pyrazine ring, indole ring, quinoline ring, xanthene ring, etc., examples of substituents include aliphatic groups, aromatic groups, acyl groups , Alkoxy groups, carbamoyl groups, sulfamoyl groups, alkylsulfonylamino groups, alkoxycarbonylamino groups, sulfonic acid groups, carboxylic acid groups, and the like. As the heterocyclic oxy group, a pyrrolyloxy group, a pyrazolyloxy group, an imidazolyloxy group, a pyrazinyloxy group, a pyrimidyloxy group, a pyridiminyloxy group, and the like are preferable.

In the general formula (Y1) and the following general formula (K1), the alkoxycarbonyloxy group includes an alkoxycarbonyloxy group having a substituent and an unsubstituted alkoxycarbonyloxy group. The alkoxy moiety preferably has 2 to 16 carbon atoms. Examples of the substituent include an aliphatic group, an aromatic group, an acyl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkylsulfonylamino group, and an alkoxycarbonylamino group. Groups, sulfonic acid groups, carboxylic acid groups and the like. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propyloxycarbonyloxy group, a cyclohexyloxycarbonyloxy group, an isobutyloxycarbonyloxy group, and a 2-ethylhexyloxycarbonyloxy group. included.
In the above general formula (Y1) and the following general formula (K1), the aryloxycarbonyloxy group includes an aryloxycarbonyloxy group having a substituent and an unsubstituted aryloxycarbonyloxy group. The aryl moiety preferably has 6 to 24 carbon atoms, and examples of the substituent include an aliphatic group, an aromatic group, an acyl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkylsulfonylamino group, and an alkoxycarbonylamino group. Groups, sulfonic acid groups, carboxylic acid groups and the like. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy group, 4-nitrophenoxycarbonyloxy group, 2-methoxyphenoxycarbonyloxy group, 2,4-dichlorophenoxycarbonyloxy group and the like.
In the above general formula (Y1) and the following general formula (K1), the substituent of “substituted amino group substituted with an alkyl group, aryl group or heterocyclic group” may further have a substituent. Unsubstituted amino groups are not included. As an alkylamino group, a C1-C6 alkylamino group is preferable. Furthermore, an ionic hydrophilic group is contained in the example of a substituent when it has a substituent. Examples of the alkylamino group include a methylamino group and a diethylamino group. The arylamino group includes an arylamino group having a substituent and an unsubstituted arylamino group. As the arylamino group, an arylamino group having 6 to 12 carbon atoms is preferable. Furthermore, examples of the substituent when having a substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

In the general formula (Y1) and the following general formula (K1), the acylamino group includes an acylamino group having a substituent. The acylamino group is preferably an acylamino group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.
In the general formula (Y1) and the following general formula (K1), the ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 12 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.
In the above general formula (Y1) and the following general formula (K1), the sulfamoylamino group includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include an N, N-dipropylsulfamoylamino group.
In the general formula (Y1) and the following general formula (K1), the alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.
In the general formula (Y1) and the following general formula (K1), the aryloxycarbonylamino group includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. As the aryloxycarbonylamino group, an aryloxycarbonylamino group having 7 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

In the general formula (Y1) and the following general formula (K1), the alkylsulfonylamino group and the arylsulfonylamino group include a substituted alkyl and arylsulfonylamino group, and an unsubstituted alkyl and arylsulfonylamino group. It is. As the sulfonylamino group, a sulfonylamino group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonylamino group include a methanesulfonylamino group, an N-phenylmethanesulfonylamino group, a benzenesulfonylamino group, and a 3-carboxybenzenesulfonylamino group.
The alkylthio group, arylthio group and heterocyclic thio group include an alkylthio group having a substituent, an arylthio group and a heterocyclic thio group and an unsubstituted alkylthio group, an arylthio group and a heterocyclic thio group. As an alkylthio group, an arylthio group, and a heterocyclic thio group, a C1-C12 thing is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl, aryl or heterocyclic thio group include a methylthio group, a phenylthio group, and a 2-pyridylthio group.
Examples of the alkylsulfonyl group and the arylsulfonyl group include a methanesulfonyl group and a phenylsulfonyl group, respectively.
Examples of the alkylsulfinyl group and the arylsulfinyl group include a methanesulfinyl group and a phenylsulfinyl group, respectively.
The sulfamoyl group includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

In the general formula (Y1), R ^a1 represents an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or Represents a sulfamoyl group.

The aliphatic group represented by R ^a1 may be unsubstituted or substituted, may be a saturated group or an unsaturated group, and is preferably an aliphatic group having 1 to 15 carbon atoms in total. Examples thereof include a methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, an isopropenyl group, a 2-ethylhexyl group, and a cyclohexyl group.
The aryl group represented by R ^a1 may be unsubstituted or substituted, and an aryl group having 6 to 16 carbon atoms is preferable. For example, phenyl group, 4-nitrophenyl group, 2-nitrophenyl group, 2-chlorophenyl group, 2,4-dichlorophenyl group, 2,4-dimethylphenyl group, 2-methylphenyl group, 4-methoxyphenyl group, 2 -Methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group and the like.
The heterocyclic group represented by R ^a1 may be a saturated or unsaturated ring group, and is preferably a heterocyclic group having 3 to 15 carbon atoms in total. For example, 3-pyridyl group, 2-pyridyl group, 2-pyrimidinyl group, 2-pyrazinyl group and the like can be mentioned.
The acyl group represented by R ^a1 may be an arylcarbonyl group or an aliphatic carbonyl group, and preferably has 2 to 15 carbon atoms in total. For example, acetyl group, pivaloyl group, benzoyl group and the like can be mentioned.
The aliphatic oxycarbonyl group represented by R ^a1 may be unsubstituted or substituted, may be a saturated group or an unsaturated group, and is an aliphatic oxycarbonyl group having 1 to 16 carbon atoms in total. preferable. For example, a methoxycarbonyl group, a butoxycarbonyl group, etc. are mentioned.
The aryloxycarbonyl group represented by R ^a1 may be unsubstituted or substituted, and is preferably an aryloxycarbonyl group having 7 to 17 carbon atoms in total. For example, a phenoxycarbonyl group etc. are mentioned.

The carbamoyl group represented by R ^a1 may be unsubstituted or substituted, and is preferably a carbamoyl group having 1 to 12 carbon atoms in total. For example, a carbamoyl group, a dimethylcarbamoyl group, etc. are mentioned.
The aliphatic sulfonyl group represented by R ^a1 may be unsubstituted or substituted, may be a saturated group or an unsaturated group, and the total number of carbon atoms in the aliphatic moiety is preferably 1-15. Examples include a methanesulfonyl group, a butanesulfonyl group, a methoxyethanesulfonyl group, and the like.
The arylsulfonyl group represented by R ^a1 may be unsubstituted or substituted, and is preferably an arylsulfonyl group having 6 to 16 carbon atoms in total. For example, a phenylsulfonyl group, 4-t-butylphenylsulfonyl group, 4-toluenesulfonyl group, 2-toluenesulfonyl group and the like can be mentioned.
The sulfamoyl group represented by R ^a1 may be unsubstituted or substituted, and is preferably a sulfamoyl group having 0 to 12 carbon atoms in total. For example, a sulfamoyl group, a dimethylsulfamoyl group, etc. are mentioned.

Among the above, from the viewpoint that the effects of the present invention can be more effectively exhibited, the R ^a1 preferably represents an aliphatic group, an aryl group, or a heterocyclic group, and more preferably represents an aryl group or a heterocyclic group. An embodiment representing an aryl group is most preferable.

In the general formula (Y1), R ^a2 represents a hydrogen atom or a substituent. X ^a1 represents —CR ^a3 = or a nitrogen atom, and R ^a3 represents a hydrogen atom or a substituent.
The substituent represented by R ^a2 or R ^a3 may be any group as long as it is a group that can be substituted as described in the above-mentioned “Substituent” section. Of these, R ^a2 and R ^a3 are each preferably the following groups from the viewpoint of more effectively achieving the effects of the present invention. That is,
R ^a2 is a hydrogen atom, aliphatic group, aryl group, acyloxy group, acylamino group, aliphatic oxy group, aliphatic sulfonyloxy group, arylsulfonyloxy group, aliphatic sulfonamido group, arylsulfonamido group, amino group, An embodiment representing an aliphatic amino group, arylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, hydroxy group, cyano group, sulfo group, carbamoylamino group, sulfamoylamino group An embodiment representing a hydrogen atom, an aliphatic group, an aryl group, an acyloxy group, an aliphatic oxy group or an aliphatic sulfonyloxy group is more preferred, and an embodiment representing a hydrogen atom or an aliphatic group is most preferred.

R ^a3 is an aliphatic group, aryl group, acyl group, acylamino group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyl group An oxy group, an arylsulfonyloxy group, an aliphatic sulfonamido group, an arylsulfonamido group, a cyano group, and a carboxy group are preferable, and X ^a1 is preferably selected from -CR ^a3 = and a nitrogen atom in the case of representing them. R ^a3 is more preferably an acyl group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a cyano group, or a carboxy group, and X ^a1 represents —CR ^a3 = and nitrogen An embodiment selected from atoms is more preferred. Furthermore, R ^a3 is most preferably an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group or a cyano group, and X ^a1 is most preferably an embodiment selected from —CR ^a3 = and a nitrogen atom.

In the general formula (Y1), B represents a coupler residue.
The coupler residue represented by B is not limited as long as it is a group capable of coupling with a diazonium salt, and examples thereof include a hydrocarbon ring group, a heterocyclic group, and a substituted methylene group. This B is a coupler in which the dye represented by the general formula (Y1) may constitute either a non-dissociation dye or a dissociation dye (a dye containing a group that becomes alkaline and dissociates and becomes a target hue). Residue. More specifically, groups represented by the following (B-1) to (B-13) are exemplified.

In the (B-1) to (B-13), R ^{a6 to} R ^a47 each represents a hydrogen atom or a substituent. The substituent here is the group described in the above-mentioned “Substituent” section, and may be any group that can be substituted. Preferred substituents include aliphatic groups, aryl groups, heterocyclic groups, acyl groups. Group, imide group, acylamino group, aliphatic oxy group, aliphatic oxycarbonyl group, carbamoyl group, sulfamoyl group, aliphatic sulfonamido group, arylsulfonamido group, amino group, aliphatic amino group, arylamino group, hydroxy group , A cyano group, a sulfo group, and a carboxy group.

^{R a6 ~R a14, R a15 ~R} a17, R a45 ~R adjacent two groups of ^a47, and R ^a19 and R ^a20, R ^a21 and R ^a22, R ^a23 and R ^a24, R ^a29 and R ^a30, R ^a31 and R ^a32, R ^a33 and R ^a34, and R ^a35 and R ^a36 is a hydrocarbon ring of 5-membered ring to 7-membered ring together as possible, it may form a heterocyclic ring.

Also, Q ^a1 of (B-9) in, Q ^a3 in (B-11) Q ^a2 and, in (B-12) is required to form each 5-membered ring to 7-membered ring together with the nitrogen atom Represents a non-metallic atomic group.

Among the above, R ^a6 and R ^a8 , R ^a11 and R ^a13 , R ^a15 and R ^a17 and R ^a18 , R ^a19 and R ^a22 , R ^a24 and R ^a25 , from the viewpoint of more effectively ^achieving the effects of the present invention. An ^{embodiment in} which at least one of R ^a26 , R ^a27 and R ^a28 each represents a hydroxy group, a substituted amino group or an arylamino group is preferred, and an embodiment in which a substituted amino group is represented is more preferred. Similarly, from the viewpoint of more effectively achieving the effects of the present invention, R ^a31 preferably represents an aliphatic group or an aryl group, and more preferably represents an aliphatic group. Similarly, from the standpoint of more effectively ^achieving the effects of the present invention, R ^a32 is preferably a hydroxy group, R ^a39 is preferably a hydroxy group or an ^optionally substituted amino group, and R ^a39 is substituted. An embodiment representing a good amino group is more preferable.

  From the standpoint that the effects of the present invention can be exhibited particularly effectively, B is preferably an embodiment that represents (B-1), (B-3), (B-6), or (B-7).

  Furthermore, among the dyes represented by the general formula (Y1), the dye represented by the following general formula (Y1-1) is more preferable from the viewpoint of the effect of the present invention.

In Formula ^{(Y1-1), R a1, R} a2, X a1, and R ^a3 has the same meaning as ^{R a1, R a2, X a1} , and R ^a3 in the above general formula (Y1), The same applies to each preferred embodiment.
In the general formula (Y1-1), B ^a1 represents —CR ^a4 = or a nitrogen atom, B ^a2 represents —CR ^a5 = or a nitrogen atom, and B ^a1 and B ^a2 do not represent a nitrogen atom at the same time. R ^a4 and R ^a5 represent a hydrogen atom or a substituent. In general formula (Y1-1), R ^a1 and R ^a2 , R ^a2 and R ^a3 , R ^a4 and R ^a5 , and R ^a5 and G ^a2 are bonded to each other to form a 5-membered ring to a 7-membered ring. Also good.

The substituent represented by R ^a4 or R ^a5 is the group described in the above-mentioned “Substituent” section and may be any group that can be substituted. From the viewpoint of more effectively achieving the effects of the present invention, R ^a4 and R ^a5 are each a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an imide group, an acylamino group, an aliphatic oxy group, an aliphatic group. A preferable embodiment is an oxycarbonyl group, carbamoyl group, sulfamoyl group, aliphatic sulfonamido group, arylsulfonamido group, amino group, aliphatic amino group, arylamino group, hydroxy group, cyano group, sulfo group or carboxy group. R ^a4 is more preferably a hydrogen atom, aliphatic group, aliphatic amino group, or arylamino group, and R ^a5 is more preferably a hydrogen atom, cyano group, or carbamoyl group.

In General Formula (Y1-1), an embodiment in which B ^a1 represents -CR ^a4 = and B ^a2 represents -CR ^a5 = or a nitrogen atom is preferable. When B ^a1 represents -CR ^a4 = and B ^a2 represents -CR ^a5 =, an embodiment in which R ^a4 represents an aliphatic group and R ^a5 represents a hydrogen atom or a cyano group is most preferable.

In the general formula (Y1-1), G ^a1 and G ^a2 each independently represent a hydrogen atom or a substituent. Substituents represented by G ^a1 or G ^a2 is a group that has been described in the "substituent" described above, and may be any substitutable group. G ^a1 and G ^a2 are each a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group from the viewpoint of more effectively achieving the effects of the present invention. , Heterocyclic oxy group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonyl An embodiment representing an amino group, a heterocyclic oxycarbonylamino group, an aliphatic thio group, an arylthio group, a heterocyclic thio group, a hydroxy group, a carbamoylamino group, a sulfamoylamino group, or a halogen atom is preferable, and a heterocyclic group or an acylamino group , Aliphatic oxy group, aryloxy group, aliphatic sulfonamido group, aryl More preferred is a sulfonamide group, an aliphatic amino group, an arylamino group, a heterocyclic amino group, an aliphatic thio group, an arylthio group, or a halogen atom, an aliphatic oxy group, an aliphatic amino group, an arylamino group, a heterocyclic ring An embodiment representing an amino group or an aliphatic thio group is more preferred, and an embodiment in which at least one of G ^a1 and G ^a2 represents an aliphatic amino group, an arylamino group, or a heterocyclic amino group is particularly preferred.

R ^a1 and R ^a2, R ^a2 and R ^a3, R ^a4 and R ^a5 and R ^a5 and G ^a2 may be a non-aromatic ring be 5- to 7-membered ring (an aromatic ring bonded to each other, carbon It may be a ring or a heterocyclic ring, and may form a benzene ring, a pyridine ring, etc.).

  Furthermore, among the dyes represented by the general formula (Y1), compounds represented by the following general formula (Y1-2) or the following general formula (Y1-3) are particularly preferable.

In the general formulas (Y1-2) and (Y1-3), R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 , X ^a1 , G ^a1 , and G ^a2 are the same as those in the general formula ( It is synonymous with R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 , X ^a1 , G ^a1 , and G ^{a2 in} Y1) or general formula (Y1-1), and these preferable embodiments are also the same.

In the general formula (Y1-2), R ^a1 represents an aliphatic group, an aryl group, or a heterocyclic group, and R ^a2 represents a hydrogen atom, an aliphatic group, or an aryl from the viewpoint of more effectively achieving the effects of the present invention. A group, an aliphatic oxy group, a hydroxy group, wherein X ^a1 is —CR ^a3 ═, and R ^a3 is an acyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a cyano group R ^a4 represents a hydrogen atom or an aliphatic group, R ^a5 represents a hydrogen atom, a cyano group or a carbamoyl group, and G ^a1 and G ^a2 represent a heterocyclic group, an acylamino group, an aliphatic oxy group, an aryloxy group Preferred is an embodiment that represents an aliphatic sulfonamido group, an arylsulfonamido group, an aliphatic amino group, an arylamino group, a heterocyclic amino group, an aliphatic thio group, an arylthio group, a hydroxy group, or a halogen atom. R ^a1 represents an aryl group, R ^a2 represents a hydrogen atom or an aliphatic group, X ^a1 represents —CR ^a3 ═, R ^a3 represents a cyano group, R ^a4 represents an aliphatic group, An embodiment in which R ^a5 represents a hydrogen atom and a cyano group, and G ^a1 and G ^a2 represent an aliphatic amino group, an arylamino group, and a heterocyclic amino group is most preferable.

In the general formula (Y1-3), R ^a1 represents an aliphatic group, an aryl group, or a heterocyclic group, and R ^a2 represents a hydrogen atom or an aliphatic group from the viewpoint of more effectively achieving the effects of the present invention. , An aryl group, an aliphatic oxy group, and a hydroxy group, wherein X ^a1 is a nitrogen atom or —CR ^a3 ═, and R ^a3 is an acyl group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, aryl Represents a sulfonyl group, a cyano group, and R ^a4 is a hydrogen atom, aliphatic group, aliphatic amino group, acylamino group, aliphatic sulfonamido group, arylsulfonamido group, aliphatic oxy group, arylamino group, aliphatic thio group , An arylthio group, a halogen atom, and G ^a1 and G ^a2 are a hydrogen atom, an aliphatic group, a heterocyclic group, an acylamino group, an aliphatic oxy group, an aryloxy group, an aliphatic sulfonamide group, An arylsulfonamide group, an aliphatic amino group, an arylamino group, a heterocyclic amino group, an aliphatic thio group, an arylthio group, a hydroxy group, or a halogen atom, and at least one of R ^a4 , G ^a1 and G ^a2 is an aliphatic amino group An embodiment representing a group, an arylamino group, or a heterocyclic amino group is preferred.

When the compound represented by the general formula (Y1), (Y1-1), (Y1-2) or (Y1-3) is a water-soluble dye, B, R ^a1 , R ^a2 , G ^a1 and It is preferable to further have an ionic hydrophilic group as a substituent at any position on ^Ga2 . The ionic hydrophilic group as a substituent includes a sulfo group, a carboxy group, a quaternary ammonium group, and the like. As the ionic hydrophilic group, a carboxy group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxy group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include an alkali metal ion (for example, sodium ion, potassium ion) and an organic cation (for example, tetramethylguanidinium ion). It is.

  Hereinafter, specific examples (exemplary compounds Y-1 to Y-) of the compounds (dyes according to the present invention) represented by the general formula (Y1), (Y1-1), (Y1-2) or (Y1-3) 78). However, the present invention is not limited to these.

  The synthesis of the compound represented by the general formula (Y1) can be performed with reference to, for example, the methods described in paragraph numbers [0120] to [0126] of JP-A-2006-47581.

~~ Compound represented by formula (K1) ~~
The case where at least one compound represented by the following general formula (K1) is contained is preferable.

In Formula (K1), Ry ₁ represents an aliphatic group, an aryl group, a heterocyclic group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or Represents a sulfamoyl group. When there are two or more Ry ₁ , the plurality of Ry ₁ may be the same or different.

The aliphatic group represented by Ry ₁ may be unsubstituted or substituted, may be saturated or unsaturated, and is an aliphatic group having 1 to 25 carbon atoms in total. Preferably, an aliphatic group having 1 to 12 carbon atoms is more preferable. Examples thereof include a methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, an isopropenyl group, a 2-ethylhexyl group, a 3-methoxypropyl group, and a 2-methoxyethyl group.

The aryl group represented by Ry ₁ may be unsubstituted or substituted, and is preferably an aryl group having 6 to 16 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. For example, a phenyl group, 4-nitrophenyl group, 4-methylphenyl group, etc. are mentioned.

The heterocyclic group represented by Ry ₁ may be saturated or unsaturated, and is a 5- to 7-membered ring having 2 to 15 carbon atoms (more preferably 2 to 12 carbon atoms in total). ) Is preferred. For example, 2-pyridyl group, 3-furyl group, 2-piperidyl group and the like can be mentioned. Moreover, you may have a substituent.

The carbamoyl group represented by Ry ₁ is preferably a carbamoyl group having 1 to 12 carbon atoms, and more preferably a carbamoyl group having 1 to 10 carbon atoms. For example, a dimethylcarbamoyl group, an ethoxyethylcarbamoyl group, etc. are mentioned.

The aliphatic oxycarbonyl group represented by Ry ₁ may be unsubstituted or substituted, may be saturated or unsaturated, and has 2 to 16 carbon atoms in total. An oxycarbonyl group is preferable, and an aliphatic oxycarbonyl group having 2 to 12 carbon atoms is more preferable. For example, a methoxycarbonyl group, a butoxycarbonyl group, etc. are mentioned.

The aryloxycarbonyl group represented by Ry _1, unsubstituted at even may have a substituent, an aryloxy carbonyl group having 7 to 17 carbon atoms are preferred, the total carbon number of 7 to 15 aryloxy A carbonyl group is more preferred. For example, a phenoxycarbonyl group etc. are mentioned.

The acyl group represented by Ry ₁ may be an aliphatic carbonyl group or an arylcarbonyl group, preferably an acyl group having 2 to 15 carbon atoms, and an acyl group having 2 to 10 carbon atoms. Is more preferable. For example, acetyl group, pivaloyl group, benzoyl group and the like can be mentioned.

The aliphatic sulfonyl group represented by Ry ₁ may be unsubstituted or substituted, and is preferably an aliphatic sulfonyl group having 1 to 15 carbon atoms, and an aliphatic sulfonyl group having 1 to 12 carbon atoms. A sulfonyl group is more preferred. Examples include a methanesulfonyl group, a butanesulfonyl group, a methoxyethanesulfonyl group, and the like.

The arylsulfonyl group represented by Ry ₁ may be unsubstituted or substituted, and is preferably an arylsulfonyl group having 6 to 20 carbon atoms, and an arylsulfonyl group having 6 to 12 carbon atoms. More preferred. For example, a benzenesulfonyl group, 4-t-butylbenzenesulfonyl group, 4-toluenesulfonyl group, 2-toluenesulfonyl group and the like can be mentioned.

The sulfamoyl group represented by Ry ₁ may be unsubstituted or substituted, and is preferably a sulfamoyl group having 0 to 18 carbon atoms, and more preferably a sulfamoyl group having 0 to 12 carbon atoms. For example, a sulfamoyl group, a dimethylsulfamoyl group, etc. are mentioned.

In the general formula (K1), Ry ₂ represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. The aliphatic group, aryl group, and heterocyclic group represented by Ry ₂ have the same meanings as the aliphatic group, aryl group, and heterocyclic group represented by Ry ₁ , respectively, and preferred embodiments thereof are also the same. is there. In the case where Ry ₂ there are two or more, a plurality of Ry ₂ may be different even in the same.

In the general formula (K1), Ry ₃ and Ry ₄ each independently represent a substituent. In addition, when there are two or more Ry ₃ and Ry ₄ , the plurality of Ry ₃ and the plurality of Ry ₄ may be the same or different.

The substituent represented by Ry ₃ may be any group that can be substituted, and includes, for example, the groups described in the above-mentioned “Substituent” section, preferably an aliphatic group, an aryl group, a hetero group. A cyclic group, an acyl group, an acyloxy group, an aliphatic oxy group, an aryloxy group, a heterocyclic oxy group, an aliphatic thio group, an arylthio group, a hydroxy group, a sulfo group, a halogen atom, and the like.

The substituent represented by Ry ₄ may be any group that can be substituted, and includes, for example, the groups listed in the above-mentioned “Substituent” section, preferably an aliphatic group, an aryl group, a hetero group. Ring group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group , Arylsulfonyl group, heterocyclic sulfonyl group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group , Aryloxycarbonylamino group, aliphatic thio group, arylthio group, cyano group, E group, a nitro group, a carboxy group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a sulfamoyl carbamoyl group, carbamoyl sulfamoyl group, and the like.

Further, when a plurality of Ry ₄ are adjacent to each other, for example, bonded to adjacent carbon atoms, they may be bonded to each other to form a 5-membered to 7-membered ring, such as naphthalene. Ring, quinoline ring and the like.

Ry ₁ and Ry ₂ may be bonded to each other to form a 5- to 7-membered ring together with the nitrogen atom (N) to which Ry ₁ and Ry ₂ are bonded. Examples of the ring include a piperidine ring, a pyrrolidine ring, a morpholine ring, and an imide ring such as succinimide.

Among the above, from the viewpoint that the effects of the present invention can be further exerted, the Ry ₁ is preferably an aliphatic group, an aryl group, a carbamoyl group, an aliphatic oxycarbonyl group, or an acyl group. The aspect which is a group, an aliphatic oxycarbonyl group, or an acyl group is more preferable, and the aspect which is an aliphatic group is the most preferable. As for each of these groups, the specific groups described above can be mentioned as more preferable ones.

Similarly, from the viewpoint that the effects of the present invention can be further exerted, the Ry ₂ is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom. Similarly, the aspect in which the Ry ₃ is an aliphatic group, an aryl group, an aliphatic oxy group, an aryloxy group, an aliphatic thio group, or an arylthio group is preferable in that the effect of the present invention can be further achieved. The aspect which is an aliphatic group, an aliphatic oxy group, or an aliphatic thio group is more preferable. Similarly, Ry ₄ may be an aliphatic group, an acylamino group, an aliphatic oxy group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, in that the effect of the present invention can be further exhibited. Sulfamoyl group, aliphatic sulfonamido group, arylsulfonamido group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, cyano group, sulfo group, nitro group, carboxy group, carbamoylamino group, sulfamoylamino group, or An embodiment that is a halogen atom is preferable, and an embodiment that is an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, a sulfamoyl group, a cyano group, a nitro group, or a halogen atom is more preferable, and an aliphatic oxycarbonyl group , Carbamoyl group, aliphatic sulfonyl group, sulf Moil group, a cyano group, or aspects and most preferably a halogen atom. In the above, the specific group mentioned above about each of these groups can be mentioned as a more preferable thing.

  In the general formula (K1), the ym is preferably 3 or 2, the yn is preferably 0 or 1, and the yp is preferably an integer of 0 to 3 from the viewpoint that the effects of the present invention can be further exerted.

  Among the compounds represented by the general formula (K1), a compound represented by the following general formula (K1-1) is preferable from the viewpoint of more effectively achieving the effects of the present invention.

In the general formula (K1-1), yq and yr each independently represent an integer of 0 to 2, and yq + yr satisfies 1 or 2. The yq is preferably 0 or 1, and the yr is preferably 1 or 2 in that the effects of the present invention can be more effectively exhibited.
Further, Ry ₁ , Ry ₂ , Ry ₃ , Ry ₄ , and yp in the general formula (K1-1) have the same meanings as in the general formula (K1), and preferred embodiments are also the same.

  From the viewpoint of more effectively achieving the effects of the present invention, among the compounds represented by the general formula (K1-1), the compounds represented by the following general formula (K1-2) are preferable.

Ry ₁ , Ry ₂ , Ry ₄ , and yp in the general formula (K1-2) are respectively synonymous with those in the general formulas (K1) to (K1-1), and preferred embodiments are also the same. Further, in the general formula (K1-2), Ry ₅ represents a hydrogen atom, Ry _3, or -N (Ry ₁₎ represents Ry _2, where Ry ₁ to Ry ₃ also Formula in (K1) ~ It is synonymous with the case in (K1-1), and a preferable aspect is also the same.
In the case where Ry ₅ represents -N (Ry ₁₎ Ry _2, another -N in the general formula _{(K1-2) (Ry 1) Ry} 2 and may be the same or different.

The Ry ₅ is preferably a hydrogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic thio group, or —N (Ry ₁ ) Ry ₂ from the viewpoint that the effects of the present invention can be further exerted. An embodiment in which it is an atom, an aliphatic group, or -N (Ry ₁ ) Ry ₂ is particularly preferred. Moreover, about these each group, the specific group mentioned above can be mentioned as a more preferable thing.

In the general formula (K1-2), the Ry ₁ may be an aliphatic group, an aryl group, an aliphatic oxycarbonyl group, or an acyl group, and the Ry ₂ is a hydrogen atom or an aliphatic group, and the Ry ₅ is a hydrogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic thio group, or —N (Ry ₁ ) Ry ₂ , and the Ry ₄ is An embodiment in which the group is an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, a sulfamoyl group, a cyano group, a nitro group, or a halogen atom is preferable, and the Ry ₁ is an aliphatic group, Ry ₂ is a hydrogen atom, and Ry ₅ is a hydrogen atom, an aliphatic group, or —N (Ry ₁ ) Ry ₂ , and Ry ₄ is an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group, Aliphatic sulfonyl group Famoiru group, a cyano group, aspect a nitro group, or a halogen atom is more preferable.

  Hereinafter, specific examples (exemplary compounds K-1 to K-48) of the compounds (dyes) represented by the general formulas (K1) to (K1-2) are shown. However, the present invention is not limited to these.

  The synthesis of the compound represented by the general formula (K1) can be performed with reference to, for example, the methods described in paragraph numbers [0163] to [0167] of JP-A No. 2006-47581.

~~ Azomethine dye represented by formula (I) ~~
Moreover, it is preferable that the dye contains at least one azomethine dye represented by the following general formula (I). This dye exhibits a good magenta hue with high transmittance characteristics, has no stability over time when it is in the form of a liquid preparation or a coated film, and particularly excellent resistance to heat and light Have

In the general formula (I), R ¹ represents a hydrogen atom or a substituent.
Examples of the substituent represented by R ¹ include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably a straight chain or branched chain having 1 to 48 carbon atoms, more preferably 1 to 18 carbon atoms, Or a cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl , 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18. For example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably carbon An aryl group having a number of 6 to 48, more preferably 6 to 12. For example, phenyl, naphthyl A heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms. For example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2- Benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 12. For example, trimethylsilyl, triethylsilyl, tributylsilyl , T-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxy group, cyano group, nitro group,

  An alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms. For example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy Group (for example, cyclopentyloxy, cyclohexyloxy)), aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 12. For example, phenoxy, 1-naphthoxy), heterocyclic oxy group (Preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), silyloxy group (preferably 1 carbon atom). ~ 32, more preferably 1-12 silyloxy groups. Methylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, acetoxy, pivaloyloxy, benzoyloxy, dodeca Noyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group ( Eg cyclohexyloxycarbonyloxy)),

  An aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 18 carbon atoms, such as phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably 1 to 12. For example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy group (preferably Is a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), alkylsulfonyloxy group (preferably 1 to 38 carbon atoms, more preferably An alkylsulfonyloxy group having 12 to 12. For example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy group (preferably having 6 to 32 carbon atoms, more preferably 6 to 12 arylsulfonyloxy group). Such as phenylsulfonyloxy),

  An acyl group (preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 12. For example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having a carbon number) An alkoxycarbonyl group having 2 to 48, more preferably 2 to 12. For example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably having a carbon number of 7 to 32, more preferably An aryloxycarbonyl group having 7 to 12. For example, phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 12. For example, carbamoyl, N, N-diethylcarbamoyl, - Ethyl -N- octylcarbamoyl, N, N- dibutylcarbamoyl, N- propylcarbamoyl, N- phenylcarbamoyl, N- methyl -N- phenylcarbamoyl, N, carboxymethyl carbamoyl into N- dicyclohexylamine),

  An amino group (preferably an amino group having 32 or less carbon atoms, more preferably 12 or less. For example, amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino A group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 12 carbon atoms. For example, anilino, N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms). A heterocyclic amino group of, for example, 4-pyridylamino), a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, acetamide, benzamide, tetradecanamide, pivaloylamide, Cyclohexaneamide), ureido group (preferably having 1 to 32 carbon atoms) More preferred is a ureido group having 1 to 12. For example, ureido, N, N-dimethylureido, N-phenylureido), an imide group (preferably an imide group having 20 or less carbon atoms, more preferably 12 or less). For example, N-succinimide and N-phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 12. For example, methoxycarbonylamino, ethoxycarbonylamino, t- Butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino),

  An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenoxycarbonylamino), a sulfonamide group (preferably having 1 to 48 carbon atoms, more preferably 1 to 12. For example, methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide), sulfamoylamino group (preferably having 1 to 48 carbon atoms, more preferably A sulfamoylamino group having 1 to 12. For example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably having 1 to 48 carbon atoms, more preferably Is an azo group of 1 to 24. For example, Phenylazo, 3-pyrazolylazo), an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 12. For example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having a carbon number) It is an arylthio group having 6 to 48, more preferably 6 to 12. For example, phenylthio), a heterocyclic thio group (preferably a C1-C32, more preferably 1 to 12 heterocyclic thio group. For example, 2 -Benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms. For example, dodecanesulfinyl group), arylsulfinyl Group (preferably having 6 to 32 carbon atoms, more preferably Or an arylsulfinyl group having 6 to 12, such as phenylsulfinyl, or an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 12. For example, methylsulfonyl, ethylsulfonyl, Propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl),

  An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 12 carbon atoms. For example, phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably having 32 or less carbon atoms, more preferably 16 carbon atoms). And the following sulfamoyl groups (for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), A sulfo group, a phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 12. For example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (preferably 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms Sufi is alkanoylamino group. For example, diethoxy phosphino yl, di-octyloxy phosphinoylamino amino), and the like.

If R ¹ mentioned above is a substitutable group, the substituent represented by R ¹ are further may have a substituent represented by R ^1, have two or more substituents In some cases, the plurality of substituents may be the same or different.

In the general formula (I), R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or a substituent. The substituent represented by R ^{2 to} R ⁵ has the same meaning as the substituent represented by R ¹ , and the preferred embodiment is also the same. When R ^{2 to} R ⁵ are substitutable groups, each group represented by R ^{2 to} R ⁵ may further have a substituent represented by R ¹ , and has two or more substituents. The plurality of substituents may be the same or different.

In the general formula (I), R ⁶ and R ⁷ each independently represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The alkyl group, alkenyl group, aryl group and heterocyclic group represented by R ⁶ or R ⁷ are the alkyl group, alkenyl group, aryl group and heterocyclic group enumerated in the substituent represented by R ^1. It is synonymous and a preferable aspect is also the same.
In addition, when R ⁶ and R ⁷ are substitutable groups, each group represented by R ⁶ or R ⁷ may be further substituted with a substituent represented by R ¹ , and two or more groups When it is substituted with, a plurality of groups may be the same or different.

In the above, R ² and R ³ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁵ and R ⁷ , and R ⁶ and R ⁷ are each independently bonded to each other to form 5 member, 6 member, or A 7-membered ring may be formed. As the 5-membered, 6-membered or 7-membered ring, cyclopentene, cyclohexene, cycloheptene, dihydropyrrole, tetrahydropyridine and the like are preferable, and the ring may be substituted with the substituent represented by R ^1. . Moreover, when substituted with two or more substituents, the plurality of substituents may be the same or different.

In the general formula (I), Za and Zb each independently represent —N═ or C (R ⁸ ) ═, and R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
The alkyl group, aryl group, or heterocyclic group represented by R ⁸ has the same meaning as the alkyl group, aryl group, or heterocyclic group listed in the substituent represented by R ¹ , and is a preferable embodiment. Is the same.
Further, when the group represented by R ⁸ is a substituted group, each group represented by R ⁸ may be further substituted with a substituent represented by R ^1, at least two groups When substituted, the plurality of groups may be the same or different.

  Of the azomethine dyes represented by the general formula (I), azomethine dyes (dyes) represented by the following general formula (II) are preferable.

In the general formula (II), R ^{9 to} R ¹⁴ each independently represents a hydrogen atom or a substituent. In the general formula ^{(II), R 1, R} 2, R 3, R 4, and R ⁶ are each synonymous with R ¹ to R ⁴ and R ⁶ in Formula (I), these preferred Each aspect is also the same. Za and Zb in the general formula (II) have the same meanings as Za and Zb in the general formula (I), respectively, and preferred embodiments thereof are also the same.

The substituent represented by R ^{9 to} R ¹⁴ has the same meaning as the substituent represented by R ¹ in the general formula (I), and the preferred embodiment is also the same. Moreover, when the substituent represented by R ^{9 to} R ¹⁴ is a substitutable group, each group represented by R ^{9 to} R ¹⁴ may be further substituted with a substituent represented by R ^1. When substituted with two or more groups, the plurality of groups may be the same or different.

R ² and R ³ , R ³ and R ⁶ , R ⁶ and R ⁹ , R ⁴ and R ¹⁴ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. Good. As the 5-membered, 6-membered or 7-membered ring, cyclopentene, cyclohexene, cycloheptene, dihydropyrrole, tetrahydropyridine and the like are preferable.

When the substituent represented by R ¹ , R ² , R ³ , or R ⁴ in the general formula (II) is a substitutable group, each group represented by R ^{1 to} R ⁴ is represented by the above general formula ( It may be further substituted with a substituent represented by R ¹ in I), and when it is substituted with two or more groups, the plurality of groups may be the same or different.

  Among the azomethine dyes represented by the general formula (II), azomethine dyes represented by the following general formula (III) are more preferable.

In the general formula (III), R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Further, in the general formula (III), R ¹ ~R ⁴ and R ⁶ and R ⁹ to R ¹⁴ is, R ¹ to R ⁴ and R ⁶ and R ⁹ in the general formula (I) or (II) to R Each of them is synonymous with ^14, and these preferred embodiments are also the same.

The alkyl group, aryl group, and heterocyclic group represented by R ⁸ have the same meanings as the alkyl group, aryl group, and heterocyclic group listed in the substituent represented by R ¹ in the general formula (I), respectively. These preferred embodiments are also the same.
Each group represented by R ⁸ may be further substituted with a substituent represented by R ¹ in the general formula (I), and when it is substituted with two or more substituents, a plurality of substituents May be the same as or different from each other.

Preferred ranges of the azomethine dyes represented by the general formula (III) are as follows.
In the azomethine dye represented by the general formula (III), R ¹ is preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, a cyano group, an alkoxy group, an aryloxy group, or a heterocyclic oxy group. Carbamoyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl A sulfonyl group, a sulfamoyl group, a sulfo group, a phosphonyl group, or a phosphinoylamino group, and R ² , R ³ , and R ⁴ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, Aryl group, heterocyclic group, alkoxy group , Aryloxy group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, alkoxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, alkylthio group, arylthio group, hetero A ring thio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, a phosphonyl group, or a phosphinoylamino group, and R ⁶ is preferably an alkyl group, an alkenyl group, An aryl group or a heterocyclic group, and R ⁸ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ^{9 to} R ¹⁴ are preferably each independently a hydrogen atom or a halogen atom. , An alkyl group, or an alkoxy group.

Furthermore, in the azomethine dye represented by the general formula (III), R ¹ is preferably an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxycarbonyl group, carbamoyl group, imide group, alkylthio group, arylthio group. Group, heterocyclic thio group, alkylsulfonyl group, or arylsulfonyl group, and R ² , R ³ , and R ⁴ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryloxy group. , An alkoxycarbonyl group, a carbamoyl group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, or an arylthio group, and R ⁶ is preferably an alkyl group, an alkenyl group, an aryl group, or hetero a Hajime Tamaki, preferably as R ^8, Atom, alkyl group, an aryl group or a heterocyclic group is preferably an R ⁹ to R ^14, each independently hydrogen atom or an alkyl group.

Furthermore, in the azomethine dye represented by the general formula (III), R ¹ is preferably an alkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, carbamoyl group, alkylthio group, arylthio group, alkylsulfonyl group. Or an arylsulfonyl group, and R ² , R ³ , and R ⁴ are preferably each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, carbamoyl group, carbonamide Group, ureido group, alkoxycarbonylamino group, sulfonamido group, alkylthio group or arylthio group, R ⁶ is preferably an alkyl group or an aryl group, and R ⁸ is preferably a hydrogen atom, an alkyl group or an aryl group. , or a heterocyclic group, R ⁹ to R ¹⁴ Preferably then, each independently a hydrogen atom or an alkyl group.

Furthermore, in the azomethine dye represented by the general formula (III), R ¹ is preferably an alkyl group, and R ² , R ³ , and R ⁴ are preferably each independently a hydrogen atom, a halogen atom, An alkyl group or an alkoxy group, R ⁶ is preferably an alkyl group, R ⁸ is preferably an alkyl group, an aryl group, or a heterocyclic group, and R ^{9 to} R ¹⁴ are preferably each independently A hydrogen atom or an alkyl group.

Most preferably, in the dye represented by the general formula (III), R ¹ is a tertiary alkyl group (preferably a tertiary alkyl group having 4 to 16 carbon atoms, more preferably 4 to 8 carbon atoms. For example, t- Butyl, t-amyl, t-octyl, 1-adamantyl), and R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom) Preferably a fluorine atom or a chlorine atom), an alkyl group (preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 8. For example, methyl, ethyl, propyl, isopropyl, t -Butyl, cyclohexyl, 2-ethylhexyl) or an alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. And R ⁶ is an alkyl group (preferably an alkyl group having 1 to 18 carbon atoms, more preferably 1 to 12. For example, methyl, ethyl, propyl, Isopropyl, octyl, 2-ethylhexyl, 2-hydroxyethyl, 3-hydroxypropyl), and R ⁸ is an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms. , Ethyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, hexadecyl), an aryl group (preferably an aryl group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, for example, phenyl or naphthyl), or A heterocyclic group (preferably a heterocyclic group having 1 to 12 carbon atoms, more preferably 2 to 12 carbon atoms; For example, 2-thienyl, 4-pyridyl, 2-pyridyl, 2-imidazolyl, 3-pyrazolyl), and R ⁹ and R ¹⁰ are alkyl groups (preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms). For example, methyl, ethyl, propyl (most preferably methyl)), R ^{11 to} R ¹³ are each independently a hydrogen atom, and R ¹⁴ is an alkyl group (preferably having 1 to 8 carbon atoms). , More preferably 1 to 4. For example, methyl, ethyl, propyl (most preferably methyl)).

  Specific examples (exemplary compounds M-1 to M-84) of the azomethine dyes represented by the general formula (I) are shown below. However, the present invention is not limited to these.

  The synthesis of the azomethine dye represented by the general formula (I) can be performed with reference to, for example, the methods described in paragraph numbers [0034] to [0071] of JP-A-2006-58700.

~~ Tetraazaporphyrin dye represented by formula (A) ~~
The colored curable composition of the present invention contains at least one tetraazaporphyrin-based dye represented by the following general formula (A). This dye exhibits a good cyan hue with high transmittance characteristics, has no stability over time when it is in the form of a liquid preparation or a coated film, and is particularly resistant to heat and light. Have

In the general formula (A), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ and Z ⁴ each independently form a 6-membered ring composed of atoms selected from a carbon atom and a nitrogen atom. Represents an atomic group to be

In the general formula (A), M ¹ represents a metal, and examples of the metal include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe. And metal chlorides such as AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ .

In the general formula (A), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently an atom necessary for forming a 6-membered ring composed of atoms selected from a carbon atom and a nitrogen atom. Represents a group. The 6-membered ring may be a saturated ring or an unsaturated ring, may be unsubstituted or may have a substituent, and another 5-membered or 6-membered ring may be condensed. It may be. The 6-membered ring includes a benzene ring, a cyclohexane ring and the like.

  Of the tetraazaporphyrin dyes represented by the general formula (A), phthalocyanine dyes represented by the following general formula (B) are particularly preferable.

In the general formula (B), M ¹ has the same meaning as M ¹ in formula (A), is the same a preferred embodiment thereof.
In the general formula (B), R ^{101 to} R ¹¹⁶ each independently represents a hydrogen atom or a substituent, and the substituent represented by R ^{101 to} R ¹¹⁶ is R ^{1 in} the general formula (I) described above. And the preferred embodiments thereof are also the same. Moreover, when the substituent represented by R ^{101 to} R ¹¹⁶ is a substitutable group, the substituent represented by R ^{101 to} R ¹¹⁶ is further represented by R ¹ in the general formula (I) described above. And when having two or more substituents, the plurality of substituents may be the same or different.

Hereinafter, examples (T-1 to T-139) of the substituents represented by R ^{101 to} R ¹¹⁶ are shown. However, the present invention is not limited to these.

Next, a preferable range of the phthalocyanine dye represented by the general formula (B) will be described.
In the general formula (B), (R ¹⁰¹ and R ¹⁰⁴ ), (R ¹⁰⁵ and R ¹⁰⁸ ), (R ¹⁰⁹ and R ¹¹² ), and (R ¹¹³ and R ¹¹² ) are substituted as α-substituted (α-substituted). ¹¹⁶ ) has a substituent in at least one of the combinations, or the β-position substituent (β-substitution) is (R ¹⁰² and R ¹⁰³ ), (R ¹⁰⁶ and R ¹⁰⁷ ), (R ¹¹⁰ and R ¹¹¹ ) and at least one of the combinations of (R ¹¹⁴ and R ¹¹⁵ ) have a substituent, or as substituents at the α-position and β-position (αβ-substitution), (R ¹⁰¹ and R ¹⁰³ And / or R ¹⁰² and R ¹⁰⁴ ), (R ¹⁰⁵ and R ¹⁰⁷ and / or R ¹⁰⁶ and R ¹⁰⁸ ), (R ¹⁰⁹ and R ¹¹¹ and / or R ¹¹⁰ and R ¹¹² ), and (R ¹¹³ and R ¹¹⁵ and It is preferable that at least one combination of R ¹¹⁴ and R ¹¹⁶ ) has a substituent.

Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxy group, a cyano group, a nitro group, an alkoxy group, and an aryl group. Oxy group, heterocyclic oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, Archi Thio, arylthio group, heterocyclic thio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a sulfo group, a phosphonyl group, and a phosphinoylamino group.
Examples of M ¹ include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, TiO, and VO.

More preferably, the general formula (B) is represented by (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ ) as an α-substituted product (mono-substituted product). Or at least one of R ¹¹⁶ ) or a β-substitution (mono-substitution) (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ^111). ) And (R ¹¹⁴ or R ¹¹⁵ ).
Preferred substituents in this case include halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxy group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy Group, carbamoyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide Group, sulfamoylamino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, phosphinoy Include amino group, the ^{M 1, Zn, Pd, Cu} , Ni, Co, TiO, VO , and the like.

More preferably, in the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) At least three of them have substituents, or β-substituents are (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ) It is a compound which has a substituent in at least 3 of these.
Preferred substituents in this case include a halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxy group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxy group. Carbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, alkylsulfinyl group, Examples thereof include an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, and a sulfo group, and M ¹ includes Zn, Pd, Cu, Ni, Co, VO, and the like.

More preferably, in the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) or have the same substituent at least three out, or as β substituents (R ¹⁰² or R ^103), (R ¹⁰⁶ or R ^107), (R ¹¹⁰ or R ^111), and (R ¹¹⁴ or R ¹¹⁵ ) Having the same substituent on at least three of them, and preferred substituents are halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, hetero Ring oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, carbonamido group, ureido group, imide group, sulfonamido group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl A compound having a rusulfonyl group, a sulfamoyl group, or a sulfo group, wherein M ¹ is Zn, Pd, Cu, Ni, Co, VO, or the like.

More preferably, in the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) At least three of them have substituents, or β-substituents are (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ) At least three of them, and the substituents are all the same compound, and the substituent is a halogen atom, an alkyl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, A compound having a heterocyclic oxy group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a sulfo group, wherein M ¹ is Zn, Pd, Cu, Ni, Co, VO, or the like is there.

Most preferably, in the general formula (B), as the α-substitution, (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) At least three of them have substituents, or β-substituents are (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ) At least three of them have the same substituent, and the substituents are all the same compound, and the substituent is a halogen atom, an alkyl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a hetero group A compound having a ring oxy group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a sulfo group, wherein M ¹ is Zn, Cu, Co, VO or the like.

  Specific examples of the tetraazaporphyrin dyes represented by the general formula (A) (including the phthalocyanine dyes represented by the general formula (B)) [Exemplary compounds C-1 to C-88, Cb-1 to Cb-50 and Cc-1 to Cc-4]. However, the present invention is not limited to these.

  The synthesis of the tetraazaporphyrin-based dye represented by the general formula (A) can be performed with reference to the method described in paragraph numbers [0107] to [0113] of JP-A-2006-58700, for example. .

  The above-mentioned dyes can be used as monochromatic dyes when constituting complementary colors such as yellow, magenta, and cyan, respectively, but when constituting primary colors such as red, green, and blue, generally two or more kinds of dyes are used. They can be used in combination. In the present invention, it can be suitably used as a mixed system (mixture) in which at least two kinds of dyes having different absorption characteristics are combined, and a primary color hue can be suitably configured.

  As content in the photosensitive resin composition of dye, although it changes with dyes, 40 weight% or more is more preferable with respect to the total solid component of this composition, Furthermore, 40 to 60 weight% is preferable.

[2] Compound represented by general formula (I) or general formula (II) The photosensitive resin composition of the present invention contains at least one compound represented by general formula (I) or general formula (II). To do.
In the present invention, as a result of earnest research, by using at least one compound represented by the general formula (I) or the general formula (II) as a polymerizable monomer, high sensitivity and high adhesion strength to a substrate are achieved. It has also been found that a high-definition pattern as designed can be formed, and the occurrence of scum on the pixel can be suppressed.

（式（Ｉ）中、Ｒ¹¹及びＲ¹²は各々独立に水素原子又はメチル基を表し、Ｒ¹³は置換基Ｐ１又は末端が置換基Ｐ１で置換されたアルコキシ基を表し、Ｒ¹⁴及びＲ¹⁵は各々独立に水素原子又は無置換のアルキル基を表し、Ｒ¹⁶は、水素原子、２−クロロエチル基、メトキシエトキシエチル基又は無置換のアルキル基を表し、ｎは０又は１を表す。）

(In the formula (I), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, R ¹³ represents a substituent P 1 or an alkoxy group whose terminal is substituted with the substituent P 1, R ¹⁴ and R ¹⁵ Each independently represents a hydrogen atom or an unsubstituted alkyl group, R ¹⁶ represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group or an unsubstituted alkyl group, and n represents 0 or 1.)

（式（ＩＩ）中、Ｒ²¹及びＲ²²は各々独立に水素原子又はメチル基を表し、Ｒ²³は末端が置換基Ｐ２で置換されたアルコキシ基を表し、Ｒ²⁴及びＲ²⁵は各々独立に水素原子又は無置換のアルキル基を表し、Ｒ²⁶は、水素原子、２−クロロエチル基、メトキシエトキシエチル基又は無置換のアルキル基を表す。）

(In the formula (II), R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, R ²³ represents an alkoxy group substituted at the end with a substituent P 2, and R ²⁴ and R ²⁵ each independently And represents a hydrogen atom or an unsubstituted alkyl group, and R ²⁶ represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group, or an unsubstituted alkyl group.

The general formula (I) will be described in detail below.
R ¹¹ and R ¹² each independently represents a hydrogen atom or a methyl group. When n is 0, the substituent P1 represents an unsaturated double bond group. The substituents R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or an alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, methyl, A lower alkyl group such as ethyl is preferable, and a methyl group is more preferable.), R ¹⁴ is a methyl group and R ¹⁵ is a hydrogen atom, or a combination of R ¹⁴ and R ¹⁵ is a hydrogen atom.

The substituent R ¹⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-chloroethyl, 3-methoxy And a lower alkyl group such as methyl and ethyl is preferable, and a methyl group is more preferable. A hydrogen atom and a lower alkyl group are preferable, and a hydrogen atom is more preferable.

  The alkoxy residue formed by substituting the terminal substituent P1 is an alkyleneoxy group (for example, an alkyleneoxy group such as ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, octyleneoxy, nonyleneoxy, etc.) And a substituted alkyleneoxy group having one or more alkyleneoxy groups linked to each other and containing an ether bond such as ethyleneoxyethoxy. However, the terminal substituent P1 may be directly bonded to the aromatic ring.

When n is 1, the terminal substituent P1 of R ¹³ represents a so-called vinyl ether group. The substituents R ¹⁴ and R ¹⁵ of the substituent P 1 are each independently a hydrogen atom or an alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl). And a lower alkyl group such as methyl and ethyl is preferred, and a methyl group is more preferred.) R ¹⁴ is a methyl group and R ¹⁵ is a hydrogen atom, or a combination of both R ¹⁴ and R ¹⁵ is a hydrogen atom. preferable.

The substituent R ¹⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-chloroethyl, methoxyethoxyethyl). And a lower alkyl group such as methyl and ethyl is preferable, and a methyl group is more preferable.], A hydrogen atom and a lower alkyl group are preferable, and a hydrogen atom is more preferable. Therefore, as the substituent P1, an unsubstituted vinyloxy group which is a functional group having a high polymerization activity is generally preferably used.

  Specific examples (TP-1 to TP-50) of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

Next, general formula (II) will be described in detail.
R ²¹ and R ²² each independently represents a hydrogen atom or a methyl group.

The terminal substituent P2 of R ²³ represents a so-called acrylic group. The substituents R ²⁴ and R ²⁵ of the substituent P 2 are each independently a hydrogen atom or an alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl). R ²⁴ is a methyl group and R ²⁵ is a hydrogen atom, or a combination of both R ²⁴ and R ²⁵ is a hydrogen atom. .

The substituent R ²⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-chloroethyl, methoxyethoxyethyl). And a lower alkyl group such as methyl and ethyl is preferable, and a methyl group is more preferable.), And a hydrogen atom is preferable. Therefore, as the substituent P2, generally a functional group having high polymerization activity such as an unsubstituted acryloxy group, methacryloxy group, crotonyloxy group is preferably used.

  The alkoxy residue formed by substitution of the terminal substituent P2 is an alkyleneoxy group (for example, an alkyleneoxy group such as ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, octyleneoxy, nonyleneoxy, In addition, it represents a substituted alkyleneoxy group having one or more alkyleneoxy groups linked to each other and containing an ether bond such as ethyleneoxyethoxy.

  Specific examples (TP-51 to TP-80) of the compound represented by the general formula (II) are shown below, but the present invention is not limited thereto.

  The total content of the compound represented by the general formula (I) and the compound represented by the general formula (II) in the photosensitive resin composition of the present invention is about 0. 0 with respect to the total solid content of the composition. 01 to 50% by weight is preferable, 0.01 to 40% by weight is more preferable, and 0.01 to 30% by weight is particularly preferable. When the total content of the compound represented by the general formula (I) and the compound represented by the general formula (II) is 0.01% by weight or more, adhesion to the substrate is improved and a color filter excellent in pattern formation is formed. it can. Moreover, it is excellent in alkali developability as it is 50 weight% or less, and pattern formation can be performed easily.

[3] Other polymerizable compound The photosensitive resin composition of the present invention contains a polymerizable compound (other polymerizable compound) other than the compound represented by the general formula (I) or the general formula (II). May be. By containing a polymerizable compound other than the compound represented by the general formula (I) or the general formula (II), a polymerization curing function capable of patterning with light can be further imparted.

  As the other polymerizable compound, an addition-polymerizable compound having at least one ethylenically unsaturated double bond can be used. Specifically, at least one terminal ethylenically unsaturated bond, preferably 2 is used. It can be selected from a group of compounds having two or more. Such a compound group has what is widely known in the said industrial field | area, for example, a monomer, a prepolymer, ie, a dimer, a trimer, an oligomer, those mixtures, those copolymers, etc. There are some chemical forms.

  Examples of other polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably And esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, and amides of aliphatic polyhydric amine compounds and unsaturated carboxylic acids. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional A dehydration condensation reaction product with carboxylic acid is also preferably used. In addition, an addition reaction product of unsaturated carboxylic acid ester or amide having an electrophilic substituent such as isocyanate group or epoxy group with monofunctional or polyfunctional alcohols, amines, thiols, further halogen group, A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of the “ester of aliphatic polyhydric alcohol compound and unsaturated carboxylic acid” include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, Tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexane Diol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tria Relate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid ethylene oxide (EO) -modified triacrylate.

  Further, as methacrylic acid esters, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy -2-hydroxy Propoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaco And sorbitol tetritaconate.
Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
Furthermore, as examples of other esters, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59. Those having an aromatic skeleton described in JP-A-5241, JP-A-2-226149, and those containing an amino group described in JP-A-1-165613 are also suitable. Furthermore, the ester monomer may be used as a mixture.

  Specific examples of the monomer of the “amide of aliphatic polyvalent amine compound and unsaturated carboxylic acid” include methylene bisacrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bisacrylamide, 1,6- Examples include hexamethylene bismethacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

Also suitable are urethane-based addition-polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl groups. Specific examples thereof include two or more per molecule described in JP-B-48-41708. And a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer having a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having an isocyanate group.
^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH ··· (A)
(In general formula (A), R ⁴ and R ⁵ each independently represent a hydrogen atom or CH _3. )

  Further, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, in addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, the photosensitivity speed is high. Can be obtained.

  Other examples include polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid. And polyfunctional acrylates and methacrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 Etc. can also be mentioned. Further, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferable. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

In addition, the structure of the polymerizable compound constituting the photosensitive resin composition of the present invention, or whether it is used alone or in combination, the details of usage such as the amount of addition are in accordance with the final performance design of the photosensitive resin composition. Can be set arbitrarily. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and bifunctional or more is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). It is also effective to adjust both sensitivity and intensity by using both of these.
In addition, the compatibility and dispersibility with other components (for example, photopolymerization initiator, pigment, binder polymer, etc.) contained in the photosensitive resin composition, the selection and use method of the photopolymerizable compound is For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a support.

As content in the photosensitive resin composition of a photopolymerizable compound, the range of 5-20 weight% is preferable with respect to the total solid of a composition. In particular, a composition in which the content of the bifunctional or higher (meth) acrylate monomer with respect to the total solid content of the composition is 5 to 20% by weight is preferable.
When the content of the photopolymerizable compound is 5% by weight or more, good pattern formability and film strength are obtained while maintaining photocurability, and when it is 20% by weight or less, surface curability is appropriate. The pattern resolution is good.
Among the above, for the same reason, the content of the polymerizable compound is more preferably 5 to 15% by weight, and particularly preferably 7.5 to 12.5% by weight.

[4] Photopolymerization initiator The photosensitive resin composition of the present invention contains a photopolymerization initiator.
Moreover, the photosensitive resin composition of this invention may contain a photoinitiator individually by 1 type, or may contain 2 or more types.
The photopolymerization initiator is not particularly limited as long as it can photopolymerize the polymerizable compound, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
Moreover, as a photoinitiator used for the photosensitive resin composition of this invention, the compound which does not have a halogen atom is preferable, the initiator with a high sensitivity with respect to i line | wire is preferable, and a lophine dimer and an oxime type compound are preferable. It can be illustrated. Further, as the oxime compound, an oxime ester compound is more preferable.
The photopolymerization initiator that can be used in the present invention is a compound that absorbs actinic radiation (light) and generates a polymerization initiating species. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays.

  Examples of the oxime photopolymerization initiator include compounds represented by the following general formula (1). In addition, the oxime compound in the present invention includes the (E) isomer and the (Z) isomer, regardless of whether the oxime N—O bond is an (E) oxime compound or a (Z) oxime compound. It may be a mixture of

（式（１）中、Ｒ、Ａ及びＢは各々独立に一価の置換基を表す。）

(In formula (1), R, A and B each independently represent a monovalent substituent.)

The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Phosphinoyl group, heterocyclic group, alkylthiocarbonyl group, arylthiocarbonyl group, dialkylaminocarbonyl group, dialkylaminothiocarbonyl group and the like. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group. , Methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group or aryloxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, Acyl groups such as methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group, Group, alkylamino group such as cyclohexylamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, In addition to alkyl groups such as tert-butyl group and dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups , Mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphono group, trimethylammonium group, dimethylsulfonium group, triphenyl Phenacylphosphonium group And the like.

  The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, okdadecyl group, isopropyl group. , Isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoyl Methyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophena Sil group, 3-trifluoromethylphenacyl group, and 3-nitrophenacyl There can be exemplified.

  The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and specifically includes a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, and a 1-pyrenyl group. Group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl groups, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenenyl group, fluorenyl group , Anthryl group, bianthracenyl group, teranthracenyl group, quao -Anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, pleadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group , Rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group, and oberenyl group.

  The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, and specific examples include a vinyl group, an allyl group, and a styryl group.

  The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples include an ethynyl group, a propynyl group, and a propargyl group.

  As the alkylsulfinyl group, an alkylsulfinyl group having 1 to 20 carbon atoms is preferable, and specifically, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a hexylsulfinyl group, a cyclohexylsulfinyl group. Octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, and methoxymethylsulfinyl group.

  The arylsulfinyl group is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, and 2-methylphenylsulfinyl group. Group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group A group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, and 4-dimethylaminophenyl sulfinyl group can be exemplified.

  As the alkylsulfonyl group, an alkylsulfonyl group having 1 to 20 carbon atoms is preferable, and specifically, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a cyclohexylsulfonyl group. Octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, and perfluoroalkylsulfonyl group.

  The arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, and 2-methylphenylsulfonyl. Group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl Group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, and 4-dimethylaminophenylsulfonyl group Group can be exemplified.

  As the acyl group, an acyl group having 2 to 20 carbon atoms is preferable, and specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, and a 2-naphthoyl group. 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl group, 2-butoxybenzoyl Group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group and 4-methoxybenzoyl group can be exemplified. .

  The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyl group. Examples thereof include an oxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylamino. Phenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group , 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyl Alkoxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and, 4-methoxy phenyloxy carbonyl group can be exemplified.

  The phosphinoyl group is preferably a phosphinoyl group having 2 to 50 carbon atoms, specifically, a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropylphosphinoyl group, a diphenylphosphinoyl group, a dimethoxyphosphinoyl group. Group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, and bis (2,4,6-trimethylphenyl) phosphinoyl group.

As the heterocyclic group, an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom is preferable.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, and a trifluoromethylthiocarbonyl group. Can be illustrated.

  Specific examples of the arylthiocarbonyl group include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, and 4-dimethylaminophenylthiocarbonyl group. 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group, 3-triphenyl Fluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group, Beauty, and a 4-methoxyphenylthiocarbonyl group.

  Specific examples of the dialkylaminocarbonyl group include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

  Examples of the dialkylaminothiocarbonyl group include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.

  Among these, from the viewpoint of increasing sensitivity, as R, an acyl group is more preferable, and specifically, an acetyl group, a propanoyl group, a benzoyl group, and a toluoyl group are more preferable.

The monovalent substituent represented by A is preferably an alkyl group, an aryl group, a heterocyclic group, or a group containing a sulfur atom, and is an alkyl group or a group containing a sulfur atom. Is more preferable. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Preferred ranges of the alkyl group, aryl group and heterocyclic group in A are the same as the preferred ranges of the alkyl group, aryl group and heterocyclic group in R.
In addition, the group containing a sulfur atom in A is preferably -A ¹ -SAr. A ¹ and Ar are respectively synonymous with A ¹ and Ar in the general formula (2) described later, and preferred examples are also the same.

The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among these, as the monovalent substituent represented by B, the following structures are particularly preferable.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in General Formula (3) described later, and preferred examples are also the same.

  As the oxime photopolymerization initiator, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone or a compound represented by the general formula (1) is preferable, and 2- (O-benzoyloxime) -1 -[4- (Phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] It is more preferable to include etanone or a compound represented by the following general formula (2) (hereinafter also referred to as “specific oxime compound”), and 2- (O-benzoyloxime) -1- [4- ( Enylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, and / or More preferably, it is a compound represented by the following general formula (2).

（式（２）中、Ｒ及びＢは各々独立に一価の置換基を表し、Ａ¹は二価の有機基を表し、Ａｒはアリール基を表す。）

(In formula (2), R and B each independently represent a monovalent substituent, A ¹ represents a divalent organic group, and Ar represents an aryl group.)

R and B in the general formula (2) have the same meanings as R and B in the general formula (1), and preferred ranges thereof are also the same.
Examples of the divalent organic group represented by A ¹ include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A ¹ is substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. An alkylene group, an alkylene group substituted with an alkenyl group (eg, vinyl group, allyl group), an aryl group (eg, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl) An alkylene group substituted with a group) is preferred.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the above-described substituents.
Specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group , Quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracene Nyl group, anthraquinolyl group, phenanthryl group Triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, pleiadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentaphenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group , A heptaphenyl group, a heptacenyl group, a pyrantrenyl group, and an oberenyl group.
Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the general formula (2), it is preferable from the viewpoint of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following general formula (3).

（式（３）中、Ｒ及びＸは各々独立に一価の置換基を表し、Ａ¹及びＹは各々独立に二価の有機基を表し、Ａｒはアリール基を表し、ｎは０〜５の整数である。）

(In Formula (3), R and X each independently represent a monovalent substituent, A ¹ and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0 to 5) Is an integer.)

R, A ¹ and Ar in the general formula (3) have the same meanings as R in the general formula (1) and A ¹ and Ar in the general formula (2), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, and an arylsulfinyl group. Group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, phosphinoyl group, heterocyclic group and halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

  The alkyl group, aryl group, alkenyl group, alkynyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphinoyl group, and heterocyclic ring in X The group is an alkyl group of R in the general formula (1), an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl. It is synonymous with a group, a phosphinoyl group, and a heterocyclic group, and its preferable range is also the same.

  The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, specifically, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, or a tert-butoxy group. Pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, octadecyloxy, ethoxycarbonylmethyl, 2-ethylhexyloxycarbonylmethyl Oxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyloxy group Group, N- methyl -N- benzylaminocarbonyl methyl group, a benzyl group, and a cyano methyl group can be exemplified.

  The aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms, and specifically includes a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, and 2-methylphenyloxy. Group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, 4-fluorophenyloxy Group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, and 4-phenylsulfanylphenyloxy group.

  As the acyloxy group, an acyloxy group having 2 to 20 carbon atoms is preferable. Specifically, an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, a trifluoromethylcarbonyloxy group, a benzoyloxy group , 1-naphthylcarbonyloxy group, and 2-naphthylcarbonyloxy group.

  As the alkylsulfanyl group, an alkylsulfanyl group having 1 to 20 carbon atoms is preferable, and specifically, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a cyclohexylsulfanyl group. Octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, and methoxymethylsulfanyl group.

  The arylsulfanyl group is preferably an arylsulfanyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfanyl group, a 1-naphthylsulfanyl group, a 2-naphthylsulfanyl group, a 2-chlorophenylsulfanyl group, and 2-methylphenylsulfanyl. Group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group A group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfanyl group, and 4-dimethylamino-phenylsulfanyl group can be exemplified.

  The carbamoyl group is preferably a carbamoyl group having 1 to 30 carbon atoms, specifically, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an N-butylcarbamoyl group, or an N-hexylcarbamoyl group. Group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2-chlorophenylcarbamoyl group, N 2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N- 4-metoki Phenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group N, N-dibutylcarbamoyl group and N, N-diphenylcarbamoyl group.

  The sulfamoyl group is preferably a sulfamoyl group having 0 to 30 carbon atoms, specifically, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, or an N, N-dialkylsulfamoyl group. N, N-diarylsulfamoyl group, and N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Preferred examples include a group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, and N, N-diphenylsulfamoyl group.

The amino group is preferably an amino group having 0 to 50 carbon atoms, and specifically includes an amino group (—NH ₂ ), an N-alkylamino group, an N-arylamino group, an N-acylamino group, and an N-sulfonyl group. Examples include an amino group, an N, N-dialkylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, and an N, N-disulfonylamino group. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) An amino group, an N, N- (dibutylsulfonyl) amino group, an N, N- (diphenylsulfonyl) amino group, a morpholino group, and 3,5-dimethyl-morpholino group, a carbazole group can be preferably exemplified.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among these, X is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylsulfanyl group, an arylsulfanyl group, from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region, An amino group is preferred.
Moreover, n in General formula (3) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the general formula (3).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  The specific oxime compound is preferably a compound represented by the following general formula (4).

（式（４）中、Ｒ及びＸは各々独立に一価の置換基を表し、Ａ¹は二価の有機基を表し、Ａｒはアリール基を表し、ｎは０〜５の整数である。）

(In the formula (4), R and X each independently represent a monovalent substituent, A ¹ represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5. )

R in the general formula (4), A ^1, Ar, X, and, n is the R in the general formula (1), the general formula (2) in A ¹ and Ar, and, in the general formula (3) X and n have the same meanings, and preferred examples are also the same.

  Specific examples (K-1) to (K-88) of the specific oxime compound in the present invention are shown below, but are not limited thereto.

  The specific oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly has high absorbance at 365 nm and 455 nm. preferable. In particular, since the specific oxime compound has an absorption in a long wavelength region as compared with a conventional oxime compound, it exhibits excellent sensitivity when exposed to a light source of 365 nm or 405 nm.

From the viewpoint of sensitivity, the specific oxime compound preferably has a molar extinction coefficient at 365 nm or 405 nm of 10,000 to 300,000, more preferably 15,000 to 300,000, and 20,000. Particularly preferred is ~ 200,000.
In the present invention, a known method can be used for the molar extinction coefficient of the compound. Specifically, for example, in an ultraviolet-visible spectrophotometer (Vary Inc., Carry-5 spectrophotometer), an ethyl acetate solvent is used. Is preferably measured at a concentration of 0.01 g / L.

  The specific oxime compound can be synthesized, for example, by the method shown below, but is not limited to this method.

  In addition to the oxime compound, the photopolymerization initiator that can be used in the present invention includes, for example, at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3 -Aryl substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and the like. Among these, it is preferable to use a halomethyl-s-triazine compound in addition to the oxime compound.

  Examples of the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound described in JP-B-57-6096, 2-trichloromethyl-5-styryl-1, and the like. , 3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3 , 4-oxadiazole and the like.

  Examples of the halomethyl-s-triazine compound include a vinyl-halomethyl-s-triazine compound described in JP-B-59-1281 and 2- (naphth-1-yl) -4 described in JP-A-53-133428. , 6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specific examples of the halomethyl-s-triazine compound include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4- Methylenedioxyphenyl) -1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1- Yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-butoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s -Triazine, 2- [4- (2-methoxyethyl) naphth-1-yl] -4,6-bis (trichloromethyl) -s-triazine,

  2- [4- (2-Ethoxyethyl) naphth-1-yl] -4,6-bis (trichloromethyl) -s-triazine, 2- [4- (2-butoxyethyl) naphth-1-yl]- 4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (6-methoxy-5- Methylnaphth-2-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (6-methoxynaphth-2-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (5-methoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4,7-dimethoxynaphth-1-yl) -4,6-bis (trichloromethyl)- s-triazine, 2- 6-Ethoxynaphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s- Triazine,

  4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

  4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

  4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (tri Roromechiru) -s- triazine,

  4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (tri Roromechiru) -s- triazine,

  4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN) Chloroethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical, T manufactured by PANCHIM Series (for example, T-OMS, T-BMP, TR, TB), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Ciba Specialty Chemicals) Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2 -Octanedione, 1- O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o- Methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercapto Eniru) -4,5-diphenyl imidazolyl dimer, can benzoin isopropyl ether also preferably used.

Moreover, the photosensitive resin composition of this invention can use a sensitizer and a light stabilizer together.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) ) Phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, and tinuvin 1130, 400. .

In addition to the above-mentioned photopolymerization initiator, other known initiators can be used for the photosensitive resin composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Thial-s-triazine compounds can be mentioned.

  Among the photopolymerization initiators, an oxime compound is preferable, an oxime ester compound is more preferable, and 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl is preferable in that the sensitivity can be increased by adding a small amount. ] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is most preferred.

  As content of the photoinitiator in the photosensitive resin composition of this invention, 0.1-10.0 weight% is preferable with respect to the total solid of this composition, More preferably, 0.5- 5.0% by weight. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

  In addition to the above components, it is preferable to add a thermal polymerization inhibitor to the photosensitive resin composition of the present invention. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

[5] Alkali-soluble resin The photosensitive resin composition of the present invention can be constituted using an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble resin is preferably a linear organic high molecular polymer and soluble in an organic solvent and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.

  In addition to the above, alkali-soluble resins include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinyl Pyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful.

  Further, the linear organic polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, glycerol (meth) acrylates, (meth) acrylamides, N-methylol (meth) acrylamides, secondary or tertiary alkyl (meth). Acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (Meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, or the like can be given.

  Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric acid ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, group derived from sulfonic acid and its salts, morpholinoethyl group, etc. Monomers containing are also useful.

  Further, the alkali-soluble resin may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful.

  Examples of the polymer having a polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble resins, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include a copolymer obtained by polymerization of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, and (meth) acrylamide, and a commercially available product. KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.

As the alkali-soluble resin, a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1,000 to 2 × 10 ⁵ is preferable from the viewpoint of developability, liquid viscosity, and the like, and 2,000 to 1 is preferable. A polymer of × 10 ⁵ is more preferable, and a polymer of 5,000 to 5 × 10 ⁴ is particularly preferable.

  The content of the alkali-soluble resin in the photosensitive resin composition of the present invention is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the total solid content of the composition, from the viewpoint of developability and the like. Preferably, 30 to 70% by weight is particularly preferable.

[6] Solvent The photosensitive resin composition of the present invention can be constituted using a solvent.
The solvent is basically not particularly limited as long as the solubility of each component and the applicability of the photosensitive resin composition are satisfied, but it should be selected in consideration of the solubility, applicability, and safety of the binder. Is preferred. Moreover, when preparing the photosensitive resin composition of this invention, it is preferable that at least 2 type of solvent is included.

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like;

  3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-ethyl-oxobutanoic acid, and the like;

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

  Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene are preferred.

  As described above, these organic solvents may be used in combination of two or more from the viewpoints of the solubility of the ultraviolet absorber and the alkali-soluble resin, the improvement of the coated surface, and the like, in particular, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene A mixed solution composed of two or more selected from glycol methyl ether acetate is preferably used.

  The content of the organic solvent in the photosensitive resin composition of the present invention is preferably an amount such that the total solid concentration of the composition is 5 to 80% by weight from the viewpoint of coatability, and 5 to 60% by weight. Is more preferable, and 10 to 50% by weight is particularly preferable.

[7] Other additives In the photosensitive resin composition of the present invention, various additives such as a filler, a polymer compound other than those described above, a surfactant, an adhesion promoter, an antioxidant are added as necessary. Further, an aggregation preventing agent or the like can be blended.

  Specific examples of these additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; and anti-aggregation agents such as sodium polyacrylate.

The photosensitive resin composition of the present invention is an organic carboxylic acid, preferably having a molecular weight of 1, in order to promote alkali solubility in the ultraviolet-irradiated part of the photosensitive resin composition and to further improve developability. An organic carboxylic acid having a low molecular weight of 000 or less can be contained.
Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid Aliphatic dicarboxylic acids such as acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid Acid; Aliphatic tricarboxylic acid such as tricarballylic acid, aconitic acid, and camphoronic acid; Aromatic monocarboxylic acid such as benzoic acid, toluic acid, cumic acid, hemellitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellito Aromatic polycarboxylic acids such as acids, trimesic acid, merophanoic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid It is done.

  The photosensitive resin composition of the present invention is used for forming colored pixels such as a color filter used in a liquid crystal display (LCD), a solid-state imaging device (for example, CCD, CMOS, etc.), an electroluminescence color filter, etc. It can be suitably used as a production application for printing ink, inkjet ink, paint, and the like.

<Color filter and manufacturing method thereof>
The method for producing a color filter of the present invention includes a step of applying the photosensitive resin composition of the present invention, a step of exposing the coated layer of the photosensitive resin composition formed by coating through a photomask, and developing. A pattern forming step.
Further, the color filter of the present invention is formed by arranging a plurality of colored or non-colored patterns on a substrate, and is produced using the photosensitive resin composition of the present invention. It can be suitably produced by the method for producing a color filter of the invention.

Specifically, as a method for producing the color filter of the present invention, a photosensitive resin composition is applied on a substrate, for example, directly or via another layer (preferably dried thereafter) to form a coating layer. (Hereinafter, this is sometimes referred to as “coating film forming step”), and the coating layer formed by coating is exposed imagewise at least with ultraviolet rays (for example, through a predetermined mask pattern). It is sometimes referred to as an “exposure step.”) The exposed coating layer is developed with a developer (for example, an alkali developer) (hereinafter, sometimes referred to as “development step”) to form a pattern. be able to. In the present invention, if necessary, a coating layer after the development treatment, that is, a step of applying heat treatment to the pattern (hereinafter also referred to as “post-baking step”) may be further provided.
Moreover, in the manufacturing method of the color filter of this invention, the hardening process hardened by further heating and / or exposing the pattern after exposure and image development can be further provided as needed.

  In the coating film forming step, the photosensitive resin composition is applied to a substrate by a coating method such as spin coating, cast coating, roll coating, slit coating, etc. (preferably dried afterwards). The resin composition layer (coating layer) is formed.

Examples of the substrate include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, and photoelectric conversion elements used for imaging elements and the like. Examples of the substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). In some cases, a black matrix for isolating each pixel pattern constituting the color filter is formed on these substrates.
Further, an undercoat layer may be provided on these substrates, if necessary, in order to improve adhesion with a layer provided on the substrate, prevent diffusion of substances, or planarize the substrate surface.

  In the exposure step, the coating layer formed in the coating film forming step is exposed imagewise in a specific pattern with at least ultraviolet rays, for example, through a mask or the like. In the exposure, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used. For color filters for liquid crystal display devices, exposure using mainly h-line and i-line is preferable for proximity exposure machines and mirror projection exposure machines, and for color filters for solid-state image sensors, i-type is mainly used for stepper exposure machines. Exposure using lines is preferred.

The exposure illuminance is preferably 10 mJ / cm ² or more, more preferably 20 mJ / cm ² or more, and more preferably 30 mJ from the viewpoint of throughput in the proximity exposure apparatus and mirror projection exposure apparatus used for the production of color filters for liquid crystal display devices. / Cm ² or more is particularly preferable. The stepper exposure machine used for manufacturing a color filter for a solid-state imaging device, also in view of the throughput is preferably 300 mJ / cm ² or more, 500 mJ / cm ² or more is more preferable, 1,000 mJ / cm ² or more is particularly preferred . The exposure amount is also from the viewpoint of throughput, preferably 1,000 mJ / cm ² or less, 500 mJ / cm ² more preferably less, 300 mJ / cm ² or less is particularly preferred.

In the developing step, the exposed coating layer is developed with a developer to reveal a pattern.
Any developer can be used as long as it dissolves the unexposed portion of the photosensitive resin composition and hardly dissolves the exposed portion (radiation irradiated portion). Specifically, various organic solvents and combinations thereof, and alkaline aqueous solutions can be used.

  Examples of the organic solvent include the solvents described above that can be used when preparing the photosensitive resin composition.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, An aqueous solution containing choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, and the like can be given.

  As the developer, it is preferable to use an alkaline aqueous solution adjusted so that the alkali concentration is preferably pH 11 to 13, more preferably pH 11.5 to 12.5. When the alkali concentration is pH 13 or less, pattern roughness, peeling, and reduction in the remaining film ratio can be avoided, and when the alkali concentration is pH 11 or more, the development speed is good and the generation of residues can be prevented.

  In the development process, development is performed using a developer such as an alkaline aqueous solution. Examples of the development method include a dipping method, a spray method, and a paddle method. The development temperature is preferably 15 to 40 ° C. Moreover, it is preferable to wash with running water after development.

  Furthermore, in the method for producing a color filter of the present invention, it is preferable that a heat treatment is performed by providing a post-baking step in order to sufficiently cure the coated layer after development. 100-300 degreeC is preferable and the heating temperature in a post-baking process has more preferable 150-250 degreeC. The heating time is preferably 10 minutes to 1 hour, more preferably 5 minutes to 30 minutes.

  The color filter of the present invention can have a plurality of patterns on a substrate, for example, a pattern in which colored pixels, a black matrix, and the like are regularly arranged. The colored pixels constituting the color filter are generally formed in a quadrilateral shape, and in this case, one side (maximum side) is preferably formed in a range of 1.5 to 200 μm. Among these, 5 μm or less is preferable, 4 μm or less is more preferable, and 3 μm or less is particularly preferable from the viewpoint of effective use of a substrate such as a silicon wafer, miniaturization of a device using a solid-state image sensor, and high-speed operation of the solid-state image sensor.

  The thickness of the colored pixel in the color filter is not particularly limited, but tends to be thin from the viewpoint of effective use of a substrate such as a silicon wafer and shading of a device using a solid-state image sensor. 2 μm or less is preferable, 1.5 μm or less is more preferable, and 1.0 μm or less is particularly preferable.

  The content of the pigment in the colored pixels constituting the color filter is not particularly limited, but is preferably 25% by weight or more based on the total solid content of the composition from the viewpoint of color separation. It is more preferably 30% by weight or more, and particularly preferably 40% by weight or more.

  The color filter of the present invention can be used as a color filter for a liquid crystal display device (LCD). However, it can be used as an image sensor such as a CCD or CMOS, particularly for a high-resolution CCD element or CMOS element exceeding 1 million pixels. It is preferable to use it. The color filter of the present invention is optimally used as, for example, a color filter disposed between a light receiving portion and a microlens for condensing light in each colored pixel constituting the CCD.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” represents “part by weight” and “%” represents “% by weight”.

Example 1
(1) Fabrication of planarization film -Preparation of planarization film resist solution-
The following components were mixed and stirred with a homogenizer stirrer to prepare a flattening film resist solution.
<Composition of resist solution for flattening film>
A solution of benzyl methacrylate / methacrylic acid (= 70/30 (molar ratio)) copolymer resin A in propylene glycol monomethyl ether acetate (45%, weight average molecular weight 30,000, manufactured by Fujikura Kasei Co., Ltd., product name: Acrylic Base FF-187) ... 22 parts dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name: KAYARAD DPHA) ... 6.5 parts propylene glycol monomethyl ether acetate (Daicel Chemical Industries, Ltd.) 13.8 parts ethyl-3-ethoxypropionate (manufactured by Nagase Sangyo Co., Ltd.) ... 12.3 parts halomethyltriazine compound (compound (T) below) ) (Manufactured by PANCHIM, product name: Triazine PP) 0.3 parts

-Fabrication of planarization film-
The obtained flattening film resist solution was applied onto a 6-inch silicon wafer by spin coating. Next, heat treatment was performed on a hot plate at a surface temperature of 120 ° C. for 120 seconds on the surface of the coating film to obtain a uniform coating film having a thickness of about 2 μm on the silicon wafer. Next, the coating film was cured in an oven at 220 ° C. for 1 hour to form a flattened film.

(2) Preparation of color filter for solid-state image sensor-Preparation of photosensitive resin composition-
Components having the following composition were mixed and dissolved to prepare a photosensitive resin composition.
· Cyclohexanone · · 80 parts · Dye A (the dye ma-1 as described above; compound represented by the general formula (M1)) · · 6.16 parts · Dye B (the dye Y-1 as described above; general Compound represented by formula (Y1)) ... 5.84 parts · KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., polymerizable monomer) ··· 5.31 parts · TP-55 (polymerizability described above) Monomer) ... 0.20 part. Photopolymerization initiator A (1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1.50 parts [IRGACURE OXE02, manufactured by Ciba Specialty Chemicals; oxime initiator]
DCMA (dicyclohexylmethylamine) 0.61 part Surfactant A (F-781, manufactured by Dainippon Ink & Chemicals, Inc.) 0.02 part

-Production of coating film-
The photosensitive resin composition obtained above was applied by spin coating on the flattened film of the silicon wafer, and then dried by heat treatment on a hot plate at a surface temperature of 100 ° C. for 120 seconds, A coating film having a thickness of about 0.6 μm after drying was formed.

−Preparation of color filter pixel pattern−
Next, with respect to the dried coating film, an illuminance of 1 at an exposure amount of 100 mJ / cm ² by an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) through an island pattern mask of 1.20 μm square. The exposure was performed at 200 mW / cm ² .

The pattern-exposed coating film was subjected to paddle development at room temperature for 60 seconds using a 60% aqueous solution of an organic alkaline developer CD-2000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.), and then spin showered for another 20 seconds. And rinsed with pure water. Thereafter, it was further washed with pure water. Thereafter, water droplets were blown off with high-pressure air, the substrate was naturally dried, and post-baked with a hot plate at 220 ° C. for 300 seconds to form a colored pattern (colored resin film) on the silicon wafer.
As described above, a color filter for a solid-state imaging device was produced.

(3) Evaluation of color filter The following evaluation and measurement were performed about the color filter for solid-state image sensors obtained from the above. The results of evaluation and measurement are shown in Table 2 below.

(3-1) Residue The pixel pattern of the color filter after post-baking is 30,000 times from the upper side of the color filter on the silicon wafer using a length measurement SEM (S-7800H, manufactured by Hitachi, Ltd.). Observation was made and the presence or absence of residue was visually evaluated according to the following evaluation criteria.
<Evaluation criteria>
○: There was no development residue.
Δ: A slight amount of development residue was observed, but was practically acceptable.
X: The generation | occurrence | production of the residue was remarkable.

(3-2) Line width The shape of the color filter pixel pattern after development and post-baking after exposure was measured on a silicon wafer using a length measurement SEM (S-7800H, manufactured by Hitachi, Ltd.). The color filter was observed from 30,000 times from above. The line width was evaluated according to the following evaluation criteria from the viewpoint of suitable dimensions compared with the 1.20 μm square pixel of the mask pattern.
<Evaluation criteria>
A: The line width was 1.05 μm or more and less than 1.35 μm.
X: The line width was less than 1.05 μm or 1.35 μm or more.

(Examples 2 to 12: Production of a color filter for a solid-state imaging device)
In Example 1, except that the composition of the photosensitive coloring composition was changed as shown in Table 1 below, a photosensitive coloring composition was prepared and a color filter was prepared in the same manner as in Example 1. Moreover, the same evaluation as Example 1 was performed. The results of evaluation and measurement are shown in Table 2 below.

(Comparative Examples 1-3: Production of color filter for solid-state imaging device)
In Example 1, except that the composition of the photosensitive coloring composition was changed as shown in Table 1 below, a photosensitive coloring composition was prepared and a color filter was prepared in the same manner as in Example 1. Moreover, the same evaluation as Example 1 was performed. The results of evaluation and measurement are shown in Table 2 below.

Details of each component in Table 1 are as follows.
Dye ma-1: Compound represented by general formula (M1) as described aboveDye Y-1: Compound represented by general formula (Y1) as described aboveDye Y-8: General formula as described above ( Y1) Compound / Dye C-1: Tetraazaporphyrin Dye / Dye M-1 Represented by General Formula (A), Azomethine System Represented by General Formula (I) Pigment
Monomer A: TO-1382 (manufactured by Toagosei Co., Ltd.)
Monomer B: TO-2360 (manufactured by Toagosei Co., Ltd.)
TP-5: polymerizable monomer described above TP-29: polymerizable monomer described above Initiator B: 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2 -Octadiene (IRGACURE OXE01, manufactured by Ciba Specialty Chemicals; oxime initiator)
Surfactant A: F-475 (Dainippon Ink & Chemicals, Inc.)

As shown in Table 2, pattern formation sensitivity is increased by using the compound represented by the general formula (I) or the general formula (II) (Examples 1 to 12 and Comparative Examples 1 to 3). Comparison).
Further, no residue is generated even when the compound represented by the general formula (I) or the general formula (II) is used.

Claims (7)

A dye, a compound represented by the following general formula (I) or the following general formula (II), and
A photosensitive resin composition comprising at least a photopolymerization initiator.

(In the formula (I), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, R ¹³ represents a substituent P 1 or an alkoxy group whose terminal is substituted with the substituent P 1, R ¹⁴ and R ¹⁵ Each independently represents a hydrogen atom or an unsubstituted alkyl group, R ¹⁶ represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group or an unsubstituted alkyl group, and n represents 0 or 1.)

(In the formula (II), R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, R ²³ represents an alkoxy group substituted at the end with a substituent P 2, and R ²⁴ and R ²⁵ each independently And represents a hydrogen atom or an unsubstituted alkyl group, and R ²⁶ represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group, or an unsubstituted alkyl group.   The total content of the compound represented by the general formula (I) and the compound represented by the general formula (II) is 0.01 to 10% by weight with respect to the total solid content of the photosensitive resin composition. The photosensitive resin composition according to claim 1.   The photosensitive resin composition of Claim 1 or 2 whose said photoinitiator is an oxime system initiator.   The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator is an oxime ester-based initiator.   The photosensitive resin composition of any one of Claims 1 thru | or 4 whose said dye is a dye which exhibits the color chosen from the group which consists of red, green, and blue. Applying the photosensitive resin composition according to any one of claims 1 to 5,
A step of exposing a coating layer of the photosensitive resin composition formed by coating through a photomask; and
A method for producing a color filter, comprising a step of forming a pattern by developing.   A color filter produced by the method for producing a color filter according to claim 6.