JP6149353B2 - Colored photosensitive resin composition - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition.

  The colored photosensitive resin composition is used for manufacturing a color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. As such a colored photosensitive resin composition, a colored photosensitive resin composition containing N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine as a polymerization initiator is known. (Patent Document 1).

JP 2010-224204 A

  In order to form a pattern using the colored photosensitive resin composition, a photolithography method is used in which the colored photosensitive resin composition is applied to a substrate, exposed through a photomask, and developed to obtain a pattern. However, in the conventionally proposed colored photosensitive resin composition, a part of the unexposed portion of the colored photosensitive resin composition layer may be peeled off during development, and the peeled piece may become a foreign matter on the pattern.

［式（１）中、Ｒ^ａ1及びＲ^ａ2は、それぞれ独立に、Ｒ^ａ11、ＯＲ^ａ11、ＣＯＲ^ａ11、ＳＲ^ａ11、ＣＯＮＲ^ａ12Ｒ^ａ13又はＣＮを表し、
Ｒ^ａ11、Ｒ^ａ12及びＲ^ａ13は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアラルキル基又は炭素数２〜２０の複素環基を表し、
Ｒ^ａ11、Ｒ^ａ12またはＲ^ａ13で表わされる基の水素原子は、ＯＲ^ａ21、ＣＯＲ^ａ21、ＳＲ^ａ21、ＮＲ^ａ22Ｒ^ａ23、ＣＯＮＲ^ａ22Ｒ^ａ23、−ＮＲ^ａ22−ＯＲ^ａ23、−Ｎ（ＣＯＲ^ａ22）−ＯＣＯＲ^ａ23、−Ｃ（＝Ｎ−ＯＲ^ａ21）−Ｒ^ａ22、−Ｃ（＝Ｎ−ＯＣＯＲ^ａ21）−Ｒ^ａ22、ＣＮ、ハロゲン原子、又はＣＯＯＲ ^ａ21で置換されていてもよく、
Ｒ^ａ21、Ｒ^ａ22及びＲ^ａ23は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアラルキル基又は炭素数２〜２０の複素環基を表し、
Ｒ^ａ21、Ｒ^ａ22またはＲ^ａ23で表される基の水素原子は、ＣＮ、ハロゲン原子、ヒドロキシ基又はカルボキシ基で置換されていてもよく、
Ｒ^ａ11、Ｒ^ａ12、Ｒ^ａ13、Ｒ^ａ21、Ｒ^ａ22またはＲ^ａ23で表される基がアルキレン部分を有する場合、該アルキレン部分は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^ａ24−、−ＮＲ^ａ24ＣＯ−、−ＮＲ^ａ24ＣＯＯ−、−ＯＣＯＮＲ^ａ24−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又は−ＣＳＯ−により１〜５回中断されていてもよく、
Ｒ^ａ24は、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアリールアルキル基又は炭素数２〜２０の複素環基を表し、Ｒ^ａ11、Ｒ^ａ12、Ｒ^ａ13、Ｒ^ａ21、Ｒ^ａ22及びＲ^ａ23で表される基がアルキル部分を有する場合、該アルキル部分は、分枝鎖状であってもよく、環状であってもよく、また、Ｒ^ａ12とＲ^ａ13及びＲ^ａ22とＲ^ａ23はそれぞれ一緒になって環を形成していてもよく、
Ｒ^ａ3及びＲ^ａ4は、それぞれ独立に、Ｒ^ａ11、ＯＲ^ａ11、ＳＲ^ａ11、ＣＯＲ^ａ11、ＣＯＮＲ^ａ12Ｒ^ａ13、ＮＲ^ａ12ＣＯＲ^ａ11、ＯＣＯＲ^ａ11、ＣＯＯＲ^ａ11、ＳＣＯＲ^ａ11、ＯＣＳＲ^ａ11、ＣＯＳＲ^ａ11、ＣＳＯＲ^ａ11、ＣＮ又はハロゲン原子を表し、
ｓ及びｔは、それぞれ独立に、０〜４の整数を表し、
Ｌは、酸素原子、硫黄原子、セレン原子、ＣＲ^ａ31Ｒ^ａ32、ＣＯ、ＮＲ^ａ33又はＰＲ^ａ34を表し、
Ｒ^ａ31、Ｒ^ａ32、Ｒ^ａ33及びＲ^ａ34は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基又は炭素数７〜３０のアラルキル基を表し、
Ｒ^ａ31、Ｒ^ａ32、Ｒ^ａ33またはＲ^ａ34で表される基がアルキル部分を有する場合、該アルキル部分は、分枝鎖状であってもよく、環状であってもよく、Ｒ^ａ31、Ｒ^ａ32、Ｒ^ａ33及びＲ^ａ34は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成していてもよく、
Ｒ^ａ5は、ヒドロキシ基、カルボキシ基又は式（２）

（式（２）中、Ｌ¹は、−Ｏ−、−Ｓ−、−ＮＲ^ａ22−、−ＮＲ^ａ22ＣＯ−、−ＳＯ₂−、−ＣＳ−、−ＯＣＯ−又は−ＣＯＯ−を表し、
Ｌ²は、炭素数１〜２０のアルキル基からｖ個の水素原子を除いた基、炭素数６〜３０のアリール基からｖ個の水素原子を除いた基、炭素数７〜３０のアラルキル基からｖ個の水素原子を除いた基又は炭素数２〜２０の複素環基からｖ個の水素原子を除いた基を表し、
Ｌ²で表される基がアルキレン部分を有する場合、該アルキレン部分は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^ａ22−、−ＮＲ^ａ22ＣＯＯ−、−ＯＣＯＮＲ^ａ22−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又は−ＣＳＯ−により１〜５回中断されていてもよく、該アルキレン部分は分枝鎖状であってもよく、環状であってもよく、
Ｒ^ａ6は、ＯＲ^ａ41、ＳＲ^ａ41、ＣＯＮＲ^ａ42Ｒ^ａ43、ＮＲ^ａ42ＣＯＲ^ａ43、ＯＣＯＲ^ａ41、ＣＯＯＲ^ａ41、ＳＣＯＲ^ａ41、ＯＣＳＲ^ａ41、ＣＯＳＲ^ａ41、ＣＳＯＲ^ａ41、ＣＮ又はハロゲン原子を表し、
Ｒ^ａ41、Ｒ^ａ42及びＲ^ａ43は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基又は炭素数７〜３０のアラルキル基を表し、Ｒ^ａ41、Ｒ^ａ42またはＲ^ａ43で表される基がアルキル部分を有する場合、該アルキル部分は分枝鎖状であってもよく、環状であってもよく、Ｒ^ａ42とＲ^ａ43は、一緒になって環を形成していてもよく、
ｖは１〜３の整数を表す。）
で表される基を表す。］ The present invention includes the following inventions.
[1] including a colorant, a resin, a polymerizable compound, and a polymerization initiator,
The resin is a polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride,
A colored photosensitive resin composition, wherein the polymerization initiator is a polymerization initiator containing a compound represented by the formula (1).

[In the formula (1), R ^a1 and R ^a2 each independently represent R ^a11 , OR ^a11 , COR ^a11 , SR ^a11 , CONR ^a12 R ^a13 or CN;
R ^a11 , R ^a12 and R ^a13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group,
The hydrogen atom of the group represented by R ^a11 , R ^a12 or R ^a13 is OR ^a21 , COR ^a21 , SR ^a21 , NR ^a22 R ^a23 , CONR ^a22 R ^a23 , —NR ^a22 —OR ^a23 , —N (COR ^a22 ) — OCOR ^a23 , —C (═N—OR ^a21 ) —R ^a22 , —C (═N—OCOR ^a21 ) —R ^a22 , CN, halogen atom, or COOR ^{a 21} may be substituted,
R ^a21 , R ^a22 and R ^a23 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group,
The hydrogen atom of the group represented by R ^a21 , R ^a22 or R ^a23 may be substituted with CN, a halogen atom, a hydroxy group or a carboxy group,
When the group represented by R ^a11 , R ^a12 , R ^a13 , R ^a21 , R ^a22 or R ^a23 has an alkylene moiety, the alkylene moiety is -O-, -S-, -COO-, -OCO-, ^{-NR a24 -, - NR a24 CO} -, - NR a24 COO -, - OCONR a24 -, - SCO -, - COS -, - OCS- or -CSO- by which it may be interrupted 1 to 5 times,
R ^a24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R ^a11 , When the group represented by R ^a12 , R ^a13 , R ^a21 , R ^a22 and R ^a23 has an alkyl moiety, the alkyl moiety may be branched, cyclic, or R ^a12 and R ^a13 and R ^a22 and R ^a23 may be combined to form a ring,
R ^a3 and ^{R a4} are each ^{independently, R a11, OR a11, SR} a11, COR a11, CONR a12 R a13, NR a12 COR a11, OCOR a11, COOR a11, SCOR a11, OCSR a11, COSR a11, CSOR a11 , CN or a halogen atom,
s and t each independently represent an integer of 0 to 4,
L represents an oxygen atom, a sulfur atom, a selenium atom, CR ^a31 R ^a32 , CO, NR ^a33 or PR ^a34 ,
R ^a31 , R ^a32 , R ^a33 and R ^a34 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms,
When the group represented by R ^a31 , R ^a32 , R ^a33 or R ^a34 has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R ^a31 , R ^a32 , R ^a33 and R ^a34 may each independently form a ring together with one of the adjacent benzene rings,
R ^a5 is a hydroxy group, a carboxy group or a formula (2)

(In the formula (2), L ¹ represents —O—, —S—, —NR ^a22 —, —NR ^{a22 CO—} , —SO ₂ —, —CS—, —OCO— or —COO—,
L ² is a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. A group in which v hydrogen atoms are removed from or a group in which v hydrogen atoms are removed from a heterocyclic group having 2 to 20 carbon atoms,
When the group represented by L ² has an alkylene moiety, the alkylene moiety is —O—, —S—, ^—COO— , ^—OCO— , —NR ^a22 —, —NR ^{a22 COO—} , —OCONR ^a22 —. , -SCO-, -COS-, -OCS- or -CSO- may be interrupted 1 to 5 times, and the alkylene moiety may be branched or cyclic,
R ^a6 represents OR ^a41 , SR ^a41 , CONR ^a42 R ^a43 , NR ^a42 COR ^a43 , OCOR ^a41 , COOR ^a41 , SCOR ^a41 , OCSR ^a41 , COSR ^a41 , CSOR ^a41 , CN or a halogen atom,
R ^a41 , R ^a42 and R ^a43 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and R ^a41 , R ^{When the} group represented by ^a42 or R ^a43 has an alkyl moiety, the alkyl moiety may be ^branched or cyclic, and R ^a42 and R ^a43 together form a ring. May be formed,
v represents an integer of 1 to 3. )
Represents a group represented by ]

[2] The colored photosensitive resin composition according to [1], wherein the colorant is a colorant containing a dye.
[3] A color filter formed from the colored photosensitive resin composition according to [1] or [2].
[4] A display device including the color filter according to [3].

  ADVANTAGE OF THE INVENTION According to this invention, when manufacturing a pattern, it becomes possible to provide the colored photosensitive resin composition with few generation | occurrence | production of the peeling piece derived from a colored photosensitive resin composition in the developing solution after image development.

  Hereinafter, the present invention will be described in detail. In addition, in this specification, the compound illustrated as each component can be used individually or in combination unless there is particular notice.

  The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the resin (A) contains an unsaturated carboxylic acid and an unsaturated carboxylic acid. It is a polymer having a structural unit derived from at least one selected from the group consisting of saturated carboxylic acid anhydrides, and the polymerization initiator (D) is a polymerization initiator containing a compound represented by the formula (1). Furthermore, it is preferable that a solvent (E) is included.

The colored photosensitive resin composition of the present invention contains a colorant (A). Examples of the colorant (A) include a dye (A1) and a pigment (A2), and the type of the colorant can be selected in accordance with the target spectrum.
The dye (A1) is not particularly limited, and a known dye can be used. Examples of the dye (A1) include oil-soluble dyes, acid dyes, amine salts of acid dyes and sulfonamides of acid dyes, and organic solvent-soluble dyes are preferable.

Examples of the dye (A1) include compounds classified as dyes by the Color Index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (Color Dyeing).
Specifically, C.I. I. Solvent Yellow 4 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 162;
C. I. Solvent red 45, 49, 125, 130;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 35, 37, 59, 67;
C. I. Solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 etc. are mentioned. In addition, C.I. I. As an acid dye, C.I. I. 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;
C. I. 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;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. 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;
C. I. Acid Violet 6B, 7, 9, 17, 19;
C. I. And dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109. In addition, C.I. I. As a direct dye, C.I. I. 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;
C. I. 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;
C. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. 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, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Examples include direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82. Furthermore, C.I. I. As a modern dye, C.I. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. 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;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern Blue 1, 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;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern dyes 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like can be mentioned.

  Examples of the dye (A1) include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, squarylium dyes, and phthalocyanine dyes.

  Especially, as a dye (A1), a xanthene dye (A1a) and an azo dye (A1b) are preferable.

  The xanthene dye (A1a) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (A1a) include C.I. I. Acid Red 51, 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 8, C.I. I. Basic Red 10 (Rhodamine B), C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, xanthene dyes described in Japanese Patent No. 4492760, and the like.

  Among these, as the xanthene dye (A1a), a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (A1a) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye (A1a).

［式（１ａ）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、−Ｒ⁸又は炭素数６〜１０の１価の芳香族炭化水素基を表す。
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜５の整数を表す。ｍが２以上の整数である場合、複数のＲ⁵は同一であるか相異なる。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表し、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
Ｒ¹¹は、それぞれ独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］
なお、式（１ａ）において、−ＳＯ₃ ^-基が存在する場合、その数は１個である。

[In Formula (1a), R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ^8, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ are the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ are bonded to each other to contain a nitrogen atom and a 3 to 10 member A heterocyclic ring may be formed.
R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]
In the formula (1a), when a —SO ₃ ^— group is present, the number is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. It is done.

In the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{1 to} R ⁴ , the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, —R ⁸ , —OH, —OR. ⁸ , —SO ₃ ⁻ , —SO ₃ H, —SO ₃ ^— Z ⁺ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ R ^8, or —SO ₂ NR ⁹ R ¹⁰ may be substituted. . Among these _{^{substituents, -SO 3 -, -SO 3 H}} , -SO 3 - is preferably at least one selected from Z ⁺ and the group consisting of _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and More preferred is at least one selected from the group consisting of —SO ₂ NR ⁹ R ¹⁰ . In this case, —SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable as —SO ₃ ⁻ Z ⁺ . When R ^{1 to} R ⁴ are these groups, the colored composition containing the compound (1a) can form a color filter with less generation of foreign matters and excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Group, decyl group, dodecyl group, hexadecyl group, icosyl group and other linear alkyl groups; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other branched chain alkyl groups; cyclopropyl group, cyclopentyl And a cycloalkyl group having 3 to 20 carbon atoms such as a group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

In the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ , a hydrogen atom contained in the saturated hydrocarbon group may be substituted with —OH or a halogen atom, —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—, —CO—, —NH— or —NR ⁸ —.

The alkyl group having 1 to 6 carbon atoms represented by R ⁶ and R ^7, among the alkyl groups listed above, include those having 1 to 6 carbon atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms represented by R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
As the ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable. When R ¹¹ is these groups, the colored composition containing the compound (1a) can form a color filter with few foreign matters.

  m is preferably 1 to 4, and more preferably 1 or 2.

  As the xanthene dye (A1a), a dye containing a compound represented by the formula (2a) (hereinafter sometimes referred to as “compound (2a)”) is more preferable. When the compound (2a) is used, the content of the compound (2a) in the xanthene dye (A1a) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (2a) as the xanthene dye (A1a).

［式（２ａ）中、Ｒ²¹〜Ｒ²⁴は、それぞれ独立に、水素原子、−Ｒ²⁶又は炭素数６〜１０の１価の芳香族炭化水素基を表す。
Ｒ²⁵は、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ１⁺又は−ＳＯ₂ＮＨＲ²⁶を表す。
ｍ１は、０〜５の整数を表す。ｍ１が２以上の整数である場合、複数のＲ²⁵は同一であるか相異なる。
ａ１は、０又は１の整数を表す。
Ｘ１は、ハロゲン原子を表す。
Ｒ²⁶は、炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｚ１⁺は、⁺Ｎ（Ｒ²⁷）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ²⁷は、それぞれ独立に、炭素数１〜２０の１価の飽和炭化水素基又はベンジル基を表す。］
なお、式（１ａ）において、−ＳＯ₃ ^-基が存在する場合、その数は１個である。

[In Formula (2a), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, —R ^26, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ²⁵ is, -SO ₃ ^- represents a Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.
m1 represents the integer of 0-5. When m1 is an integer of 2 or more, the plurality of R ²⁵ are the same or different.
a1 represents an integer of 0 or 1.
X1 represents a halogen atom.
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁷ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. ]
In the formula (1a), when a —SO ₃ ^— group is present, the number is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{21 to} R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group in R ^{1 to} R ⁴ . Hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, may be substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26.
As a combination of R ^{21 to} R ²⁴ , R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbons hydrogen atoms contained in the _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, those substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ preferred. A more preferred combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and hydrogen contained in the aromatic hydrocarbon group atom, -SO ₃ ^- in which are substituted with Z1 ⁺ or -SO ₂ NHR ^26. When R ^{21 to} R ²⁴ are these groups, the colored composition containing the compound (2a) can form a color filter having excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ^{8 to} R ¹¹ .
-R ²⁶ in R ²¹ to R ²⁴ each independently represent a hydrogen atom, a methyl group or an ethyl group. As the R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ^26, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, A 2-ethylhexyl group is more preferred. When R ²⁶ is such a group, the colored composition containing the compound (2a) can form a color filter with less generation of foreign matters.

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
As the ⁺ N (R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ²⁷ is preferably 20 to 80, 20 to 60 is more preferable. The colored composition containing the compound (2a) in which R ²⁷ is any of these groups can form a color filter with less generation of foreign matters.

  m1 is preferably 1 to 4, and more preferably 1 or 2.

Examples of the compound (2a) include compounds represented by formula (1-1) to formula (1-22). In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. Among these, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. The quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12).

  As the xanthene dye (A1a), a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) may be used. it can. Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material.

  The azo dye (A1b) is a dye containing an azo compound, and more preferably a dye containing a compound represented by the formula (1b) (hereinafter sometimes referred to as “compound (1b)”). When the compound (1b) is used, the content of the compound (1b) in the azo dye (A1b) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1b) as the azo dye (A1b).

[In Formula (1b), A ⁰ represents a C6-C14 divalent aromatic hydrocarbon group which may have a substituent.
B ⁰ represents a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent. Represent.
R ⁵¹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or an acyl group having 2 to 18 carbon atoms which may have a substituent. .
p1 represents 1 or 2. When p1 is 2, the plurality of A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same as or different from each other.
When p1 is 1, R ⁵² represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a monovalent substituent, and when p1 is 2, R ⁵² represents an optionally substituted divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, and includes the monovalent aliphatic hydrocarbon group and the divalent aliphatic hydrocarbon group. The —CH ₂ — contained may be replaced by —O—, —S—, —CO— and —NR′—.
R ′ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms. ]

  The azo dye (A1b) is a dye containing an azo compound, and more preferably a dye containing a compound represented by the formula (2b) (hereinafter sometimes referred to as “compound (2b)”). When the compound (2b) is used, the content of the compound (2b) in the azo dye (A1b) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (2b) as the azo dye (A1b).

[In formula (2b), Z ¹ , Z ² and Z ³ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent, and Z ¹ , —CH ₂ — contained in Z ² and Z ³ may be replaced by —CO— or —O—.
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a carbon number which may have 2 substituents. Represents an acyl group of ˜18.
A ¹ and A ² each independently represent a C 6-14 divalent aromatic hydrocarbon group which may have a substituent.
B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a C ^{3 to} 14 carbon group which may have a substituent. Represents a monovalent heterocyclic group. ]

Z ¹ , Z ² and Z ³ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent. Carbon number of a substituent is not contained in carbon number of a C1-C16 bivalent aliphatic hydrocarbon group, The number becomes like this. Preferably it is 2-10, More preferably, it is 2-8.
Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include alkanediyl groups having 1 to 16 carbon atoms, such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, Examples include a heptanediyl group, an octanediyl group, a decanediyl group, a tetradecanediyl group, and a hexadecanediyl group.
—CH ₂ — contained in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be replaced by —CO— or —O—. The hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with a halogen atom such as a fluorine atom.

Z ¹ and Z ² are preferably an alkanediyl group having 1 to 8 carbon atoms which may contain —O—, and an alkanediyl group having 5 to 7 carbon atoms which may contain —O—. More preferably. Preferable groups include, for example, — (CH ₂ ) ₃ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —O— (CH _{2) 2} - or _-CH 2 -CH (CH ₃₎ - and the like.
Z ³ is preferably a C 1-8 divalent aliphatic hydrocarbon group which may contain —C (═C) —, and is an unsubstituted alkanediyl group having 1 to 8 carbon atoms. More preferably, it is an unsubstituted alkanediyl group having 4 to 8 carbon atoms. Preferable groups include, for example, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, or —CH ₂ —C (═CH ₂ ) —.

The monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms representing R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number is preferably 6 to 10, more preferably 1 to 4.
Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , Methylbutyl group (such as 1,1,3,3-tetramethylbutyl group), methylhexyl group (such as 1,5-dimethylhexyl group), ethylhexyl group (such as 2-ethylhexyl group), cyclopentyl group, cyclohexyl group, methyl Examples thereof include a cyclohexyl group (such as 2-methylcyclohexyl group) and a cyclohexylalkyl group.
The hydrogen atom contained in the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxy group. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms include a propoxypropyl group (such as 3- (isopropoxy) propyl group) and an alkoxypropyl group (3- (2-ethylhexyloxy) propyl group, etc.). Examples of the C1-C16 aliphatic hydrocarbon group substituted with a carboxy group include a 2-carboxyethyl group, a 3-carboxypropyl group, and a 4- (carboxy) butyl group.

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms that may have a substituent representing R ⁵² include an alkanediyl group having 1 to 35 carbon atoms, such as a methylene group, an ethylene group, and propane. Examples thereof include a diyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a decanediyl group, a tetradecanediyl group, and a hexadecanediyl group.
—CH ₂ — contained in the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms may be replaced by —O—, —S—, —CO— or —NR′—. The hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 35 carbon atoms may be substituted with a halogen atom such as a fluorine atom.
Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms representing R ′ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.

A hydrogen atom contained in an acyl group having 2 to 18 carbon atoms representing R ⁵¹ , R ⁵³ and R ⁵⁴ may be substituted with an alkoxy group having 1 to 8 carbon atoms. The carbon number of the acyl group having 2 to 18 carbon atoms which may have a substituent is counted including the carbon number of the substituent, and the number is preferably 6 to 10. Examples of the acyl group that may have a substituent include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

R ⁵³ and R ⁵⁴ are preferably a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and an acyl group having 2 to 5 carbon atoms. Preferable groups include, for example, a hydrogen atom, an acetyl group, or a propionyl group.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms representing A ⁰ , A ¹ and A ² include a phenylene group and a naphthalenediyl group, and among them, a phenylene group is preferable.

Examples of the substituent for the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, a sulfamoyl group, and N-substituted sulfamoyl groups and the like can be mentioned.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom, a chlorine atom, or a bromine atom is preferable.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, and a methyl group is particularly preferable.

  Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group. An alkoxy group having 1 to 4 carbon atoms is preferable, an alkoxy group having 1 to 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.

N-substituted sulfamoyl groups include —SO ₂ NHR ⁵⁵ and —SO ₂ N (R ⁵⁵ ) R ⁵⁶ , and specifically, —SO ₂ NHR ⁸ and —SO ₂ N (R) in compound (1a). ⁸ ) The same groups as mentioned for R ⁹ can be mentioned. Among them, R ⁵⁵ and R ⁵⁶ are each independently an optionally substituted aliphatic hydrocarbon group having 1 to 16 carbon atoms or an optionally substituted acyl having 2 to 18 carbon atoms. The group N-substituted sulfamoyl group is preferred.

［Ｒは、水素原子又は有機基を表す。］
該有機基としては、例えば、後述のＲ^５９と同様の基が挙げられる。 B ⁰ , B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or 3 carbon atoms which may have a substituent. Represents a monovalent heterocyclic group of -14.
Examples of the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.
Examples of the monovalent heterocyclic group having 3 to 14 carbon atoms include the groups shown below.

[R represents a hydrogen atom or an organic group. ]
Examples of the organic group include the same groups as R ⁵⁹ described below.

The hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms is a hydroxy group, an oxo group, or a monovalent fatty acid having 1 to 16 carbon atoms. May be substituted with an aromatic hydrocarbon group, a cyano group, an amino group or an N-substituted amino group.
As the N-substituted amino group, —NHR ⁵⁷ group or —NR ⁵⁷ R ⁵⁸ group is preferable. However, each of R ⁵⁷ and R ⁵⁸ independently represents an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms or optionally substituted 3 to 3 carbon atoms. 14 monovalent heterocyclic groups. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms include the same groups as described above.

［式（３−ａ）中、Ｒ^５９は水素原子又は置換基を有していてもよい炭素数１〜１６の１価の脂肪族炭化水素基を表す。Ｒ^６０は、置換基を有していてもよい炭素数１〜１６の１価の脂肪族炭化水素基を表す。］
式（３−ａ）で表される基のピリドン環は、ケト型であってもエノール型であってもよい。 B ⁰ , B ¹ and B ² are preferably each independently a group represented by the formula (3-a).

[In formula (3-a), R ⁵⁹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. R ⁶⁰ represents a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. ]
The pyridone ring of the group represented by the formula (3-a) may be a keto type or an enol type.

The monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, the same thing can be mentioned as ^{the, R 59} is (such as 1,1,3,3-tetramethylbutyl group) methylbutyl group, hexyl methyl Groups (such as 1,5-dimethylhexyl group), ethylhexyl groups (such as 2-ethylhexyl group), methylcyclohexyl groups (such as 2-methylcyclohexyl group) and alkoxypropyl groups (3- (2-ethylhexyloxy)) A branched aliphatic hydrocarbon group such as a propyl group is preferable.
Examples of the substituent for R ⁵⁹ and R ⁶⁰ include a hydroxy group, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, and an acyloxy group having 1 to 8 carbon atoms. Examples of the alkoxy group having 1 to 8 carbon atoms include the same ones as described above. Examples of the acyloxy group having 1 to 8 carbon atoms include acetyloxy group, propionyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, benzoyloxy group and the like.
R ⁶⁰ is preferably a methyl group.

  Examples of the compound (2b) include compounds represented by formulas (4-1) to (4-6) and compounds described in JP2010-275531A.

B ¹ and B ² are preferably the same type of group, and more preferably A ¹ and A ² , R ⁵³ and R ⁵⁴ , and Z ¹ and Z ² are the same type of group, respectively. When these groups are used, the production of the compound (2b) is easy.
Compound (2b) can be produced by the method described in JP 2010-275531 A.

Examples of the pigment (A2) include organic pigments and inorganic pigments, and compounds classified as pigments by the color index (published by The Society of Dyers and Colorists).
Specific examples of the organic pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 242, 254, C.I. I. Pigment violet 23, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Green 7, 36, and 58 are preferable. Examples of the pigment used in the colored photosensitive resin composition of the present invention include C.I. I. Pigment blue 15: 6, C.I. I. Pigment red 254, C.I. I. Pigment red 242, C.I. I. Pigment red 177, C.I. I. Pigment green 58, C.I. I. Pigment yellow 150 and C.I. I. A pigment containing at least one selected from the group consisting of CI Pigment Yellow 138 is more preferable.

  If necessary, the pigment (A2) may be treated with rosin, surface treatment using a pigment derivative or pigment dispersant into which an acidic group or basic group has been introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid, etc. Atomization treatment by an atomization method or the like, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment by an ion exchange method of ionic impurities, or the like may be performed. The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

  Commercially available surfactants can be used as the pigment dispersant, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, non-ionic, amphoteric, polyester-based, polyamine-based, and acrylic-based. Surfactant etc. are mentioned, Each can be used individually or in combination of 2 or more types. Examples of pigment dispersants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Ajisper (Ajinomoto Fine Techno Co., Ltd.) )), Disperbyk (manufactured by Big Chemie), and the like.

  When the pigment dispersant is used, the amount used is preferably 1 part by mass or less, more preferably 0.05 part by mass or more and 0.5 part by mass or less, per 1 part by mass of the pigment (A2). When the amount of the pigment dispersant used is in the above range, it is preferable because a pigment dispersion in a uniform dispersion state tends to be obtained.

The colorant (A) preferably contains a dye (A1). In this case, content of dye (A1) is 3-100 mass% with respect to a coloring agent (A), Preferably it is 5-95 mass%, More preferably, it is 5-80 mass%.
Content of a pigment (A2) is 0-97 mass% with respect to a coloring agent (A), Preferably it is 5-95 mass%, More preferably, it is 20-95 mass%.
When the content of the dye (A1) and the pigment (A2) is in the above range, the desired spectrum can be obtained, and it tends to have excellent brightness and contrast, and excellent heat resistance and light resistance. This is preferable.

When the coating film and / or pattern formed using the colored photosensitive resin composition is used in a color filter provided in a liquid crystal display device or the like, the colored photosensitive resin composition is a blue colored photosensitive resin composition. Product, green colored photosensitive resin composition and red colored photosensitive resin composition, respectively.
The blue colored photosensitive resin composition preferably contains a xanthene dye (A1a) as the dye (A1). Further, as the pigment (A2), C.I. I. Pigment violet 23, C.I. I. Pigment blue 15: 3 and C.I. I. Preferably at least one selected from the group consisting of CI Pigment Blue 15: 6; I. More preferably, it contains CI Pigment Blue 15: 6.
When the dye (A1) is a xanthene dye (A1a), the mass ratio of the pigment (A2) and the xanthene dye (A1a) is preferably 97: 3 to 50:50, and 97: 3 to 70:30. More preferably.

The green colored photosensitive resin composition preferably contains an azo dye (A1b) as the dye (A1). Further, as the pigment (A2), C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 138 and C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Yellow 150.
When the dye (A1) is an azo dye (A1b), the mass ratio of the pigment (A2) to the azo dye (A1b) is preferably 99: 1 to 50:50, and 97: 3 to 70:30. More preferably.

  The red colored photosensitive resin composition preferably contains at least one selected from the group consisting of azo dyes, metal complex azo dyes, and xanthene dyes as the dye (A1). Further, as the pigment (A2), C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. It is preferable to contain at least one selected from the group consisting of CI Pigment Red 254.

  Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass% with respect to solid content in a colored photosensitive resin composition, More preferably, it is 8-55 mass%, More preferably, it is 10-10. 50% by mass. Here, solid content means the total amount of the component remove | excluding the solvent from the coloring photosensitive resin composition. When the content of the colorant (A) is in the above range, the color density when the color filter is obtained is sufficient, and the resin can be contained in the composition in a required amount, so that the mechanical strength is sufficient. It is preferable because it tends to form a simple pattern.

The colored photosensitive resin composition of the present invention contains a resin (B), and the resin (B) is a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. It is a polymer having. This structural unit is a structural unit produced | generated by superposing | polymerizing with the unsaturated bond which at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride.
Examples of the resin (B) include the following resins [K1] to [K6].
[K1] at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (a) (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, A copolymer with a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”).
[K2] (a), (b), and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) [K3] Copolymer of (a) and (c) [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c).
[K5] A resin obtained by reacting (a) with a copolymer of (b) and (c).
[K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

(B) has, for example, a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. It refers to a polymerizable compound. (B) is preferably a monomer having a C2-C4 cyclic ether structure and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  (B1) may be, for example, a monomer (b1-1) having a structure obtained by epoxidizing a linear or branched unsaturated aliphatic hydrocarbon (hereinafter referred to as “(b1-1)”) ), A monomer (b1-2) having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon (hereinafter sometimes referred to as “(b1-2)”).

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by formula (II).

[In Formula (I) and Formula (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
X ^a and ^{X b} are each independently a single ^{bond, -R c -, * - R} c -O -, * - R c -S -, * - represents the R c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ¹ and R ² are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, a * —CH ₂ —O— group, a * —CH ₂ CH ₂ —O— group, and more preferably a single bond, * — CH ₂ CH ₂ -O- group.
* Represents a bond with O.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) Is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) Is mentioned. More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is preferably (b1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the colored photosensitive resin composition is excellent.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;

  Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 5-60 mol%, more preferably 10-50 mol%.
Structural unit derived from (b); 40 to 95 mol%, more preferably 50 to 90 mol%.
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, solvent resistance of the resulting pattern, heat resistance, and mechanical strength tend to be excellent.
As the resin [K1], a resin in which (b) is (b1) is preferable, and a resin in which (b) is (b1-2) is more preferable.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel and heated and kept warm while stirring in a deoxygenated atmosphere, for example. . In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) As the solvent, any solvent capable of dissolving each monomer may be used, and a solvent (E) described later can be used as a solvent for the colored photosensitive resin composition.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using a solvent (D) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 4-45 mol%, more preferably 10-30 mol%.
Structural unit derived from (b); 2-95 mol%, more preferably 5-80 mol%.
Structural unit derived from (c); 1 to 65 mol%, more preferably 5 to 60 mol%.
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability, developability, solvent resistance of the resulting pattern, heat resistance, and mechanical strength tend to be excellent.
As the resin [K2], a resin in which (b) is (b1) is preferable, and a resin in which (b) is (b1-2) is more preferable.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].
Specifically, a predetermined amount of (a), (b) and (c), a polymerization initiator, and a solvent are charged into a reaction vessel, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
(A) 2 to 55 mol%, more preferably 10 to 50 mol%.
(C) 45 to 98 mol%, more preferably 50 to 90 mol%.
Resin [K3] can be manufactured by the same method as resin [K1], for example.

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
(A) 5 to 50 mol%, more preferably 10 to 45 mol%.
(C) 50 to 95 mol%, more preferably 55 to 90 mol%.

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( (Dimethylaminomethyl) phenol and the like) and a polymerization inhibitor (for example, hydroquinone and the like) are placed in a flask and reacted at, for example, 60 to 130 ° C. for 1 to 10 hours to obtain a resin [K4]. .
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol%, more preferably 10-90 mol%.
Structural unit derived from (c); 5-95 mol%, more preferably 10-90 mol%.

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (highmic acid anhydride) and the like. It is done. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Glycidyl (meth) acrylate was added to resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer such as (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic Resin such as resin obtained by adding glycidyl (meth) acrylate to acid copolymer [K4]; resin obtained by reacting (meth) acrylic acid with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer , Tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin such as a resin obtained by reacting (meth) acrylic acid with the polymer [K5]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and tetrahydro Examples thereof include a resin [K6] such as a resin reacted with phthalic anhydride.
These resins may be used alone or in combination of two or more.

Among these, as the resin (B), a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a C2-C4 cyclic ether structure, and an ethylenically unsaturated group Resin [K1] and resin [K2], which are copolymers having a structural unit derived from a monomer having a bond, are preferable, and a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond The resin [K1] and the resin [K2] are structural units derived from 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate, respectively. Is more preferable.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (B) is in the above range, the colored photosensitive resin composition tends to be excellent in coatability, and the film thickness of the exposed portion of the coating film after drying during development when forming a pattern is reduced. In addition, there is a tendency that the non-exposed portion of the coating film after drying is excellent in solubility in the developer during development.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
The acid value of the resin (B) is preferably 20 to 150 mg-KOH / g, more preferably 40 to 135 mg-KOH / g, and still more preferably 50 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 10 to 35% by mass, more preferably 15 to 30% by mass, based on the solid content in the colored photosensitive resin composition. Moreover, the content of the resin (B) is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of the resin (B) and the polymerizable compound (C). More preferably, it is 35 to 60% by mass.
When the content of the resin (B) is in the above range, the solubility in the developer is sufficient, development residue is hardly generated on the substrate of the non-pixel portion, and the pixel portion of the exposed portion is not developed during development. It is preferable because film loss is less likely to occur and the non-pixel portion tends to be easily removed. Further, it is preferable because the resolution and the remaining film ratio tend to be improved.

The colored photosensitive resin composition of the present invention contains a polymerizable compound (C).
The polymerizable compound (C) is a compound that can be polymerized by active radicals generated from the polymerization initiator (D), and is, for example, a compound having a polymerizable ethylenically unsaturated double bond, preferably ( It is a meth) acrylic acid ester compound.

  Examples of the polymerizable compound (C) having one ethylenically unsaturated double bond include the compounds mentioned as the above (a), (b) and (c), among which (meth) acrylic acid esters are preferable.

  Examples of the polymerizable compound (C) having two ethylenically unsaturated double bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol diester. (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di Meth) acrylate, 3-methyl-pentanediol di (meth) acrylate.

  Examples of the polymerizable compound (C) having three or more ethylenically unsaturated double bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meta) ) Acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripenta Lithritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, Tripentaerythritol hepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipe Taerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) Acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride, Examples include caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydrides. Among these, a tri- or higher functional monomer is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

  Content of polymeric compound (C) becomes like this. Preferably it is 7-65 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is 13-60 mass%, More preferably, 17- 55% by mass. Further, the total amount of the resin (B) and the polymerizable compound (C) is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 40 to 65% by mass. is there. If the content of the polymerizable compound (C) is in the above range, curing will occur sufficiently, the remaining film ratio in development will improve, and undercut will not easily enter the pattern, resulting in good adhesion. This is preferable.

  The colored photosensitive resin composition of the present invention contains a polymerization initiator (D). The polymerization initiator (D) includes a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”).

（式（２）中、Ｌ¹は、−Ｏ−、−Ｓ−、−ＮＲ^ａ22−、−ＮＲ^ａ22ＣＯ−、−ＳＯ₂−、−ＣＳ−、−ＯＣＯ−又は−ＣＯＯ−を表し、
Ｌ²は、炭素数１〜２０のアルキル基からｖ個の水素原子を除いた基、炭素数６〜３０のアリール基からｖ個の水素原子を除いた基、炭素数７〜３０のアラルキル基からｖ個の水素原子を除いた基又は炭素数２〜２０の複素環基からｖ個の水素原子を除いた基を表し、
Ｌ²で表される基がアルキレン部分を有する場合、該アルキレン部分は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^ａ22−、−ＮＲ^ａ22ＣＯＯ−、−ＯＣＯＮＲ^ａ22−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又は−ＣＳＯ−により１〜５回中断されていてもよく、該アルキレン部分は分枝鎖状であってもよく、環状であってもよく、
Ｒ^ａ6は、ＯＲ^ａ41、ＳＲ^ａ41、ＣＯＮＲ^ａ42Ｒ^ａ43、ＮＲ^ａ42ＣＯＲ^ａ43、ＯＣＯＲ^ａ41、ＣＯＯＲ^ａ41、ＳＣＯＲ^ａ41、ＯＣＳＲ^ａ41、ＣＯＳＲ^ａ41、ＣＳＯＲ^ａ41、ＣＮ又はハロゲン原子を表し、
Ｒ^ａ41、Ｒ^ａ42及びＲ^ａ43は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基又は炭素数７〜３０のアラルキル基を表し、Ｒ^ａ41、Ｒ^ａ42またはＲ^ａ43で表される基がアルキル部分を有する場合、該アルキル部分は分枝鎖状であってもよく、環状であってもよく、Ｒ^ａ42とＲ^ａ43は、一緒になって環を形成していてもよい。本明細書において、「Ｒ^ａ12とＲ^ａ13及びＲ^ａ22とＲ^ａ23はそれぞれ一緒になって環を形成している」とは、「Ｒ^ａ12とＲ^ａ13及びＲ^ａ22とＲ^ａ23はそれぞれ一緒になって接続する窒素原子、炭素原子または酸素原子とともに環を形成している」ことを意味する。
ｖは１〜３の整数を表す。）
で表される基を表す。］
[In the formula (1), R ^a1 and R ^a2 each independently represent R ^a11 , OR ^a11 , COR ^a11 , SR ^a11 , CONR ^a12 R ^a13 or CN;
R ^a11 , R ^a12 and R ^a13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group,
The hydrogen atoms of the groups represented by R ^a11 , R ^a12 and R ^a13 are OR ^a21 , COR ^a21 , SR ^a21 , NR ^a22 R ^a23 , CONR ^a22 R ^a23 , -NR ^a22 -OR ^a23 , -NCOR ^a22 -OCOR ^a23 , -C (= N-OR ^a21 ) -R ^a22 , -C (= N-OCOR ^a21 ) -R ^a22 , CN, a halogen atom, or COOR ^{a 21} may be substituted,
R ^a21 , R ^a22 and R ^a23 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group,
The hydrogen atom of the group represented by R ^a21 , R ^a22 and R ^a23 may be substituted with CN, a halogen atom, a hydroxy group or a carboxy group,
When the group represented by R ^a11 , R ^a12 , R ^a13 , R ^a21 , R ^a22 or R ^a23 has an alkylene moiety, the alkylene moiety is -O-, -S-, -COO-, -OCO-, ^{-NR a24 -, - NR a24 CO} -, - NR a24 COO -, - OCONR a24 -, - SCO -, - COS -, - OCS- or -CSO- by which it may be interrupted 1 to 5 times,
R ^a24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R ^a11 , When the group represented by R ^a12 , R ^a13 , R ^a21 , R ^a22 or R ^a23 has an alkyl moiety, the alkyl moiety may be branched, cyclic, or R ^a12 and R ^a13 and R ^a22 and R ^a23 may be bonded together to form a ring. In the present specification, “R ^a12 and R ^a13 and R ^a22 and R ^a23 are combined to form a ring” means “R ^a12 and R ^a13 and R ^a22 and R ^a23 are each combined. A nitrogen atom, a carbon atom or an oxygen atom connected to each other.
R ^a3 and ^{R a4} are each ^{independently, R a11, OR a11, SR} a11, COR a11, CONR a12 R a13, NR a12 COR a11, OCOR a11, COOR a11, SCOR a11, OCSR a11, COSR a11, CSOR a11 , CN or a halogen atom,
s and t each independently represent an integer of 0 to 4,
L represents an oxygen atom, a sulfur atom, a selenium atom, CR ^a31 R ^a32 , CO, NR ^a33 or PR ^a34 ,
R ^a31 , R ^a32 , R ^a33 and R ^a34 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms,
When the group represented by R ^a31 , R ^a32 , R ^a33 or R ^a34 has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R ^a31 , R ^a32 , R ^a33 and R ^a34 may independently form a ring together with one of the adjacent benzene rings. In the present specification, “R ^a12 and R ^a13 and R ^a22 and R ^a23 are combined to form a ring” means “R ^a12 and R ^a13 and R ^a22 and R ^a23 are each combined. A nitrogen atom, a carbon atom or an oxygen atom connected to each other.
R ^a5 is a hydroxy group, a carboxy group or a formula (2)

(In the formula (2), L ¹ represents —O—, —S—, —NR ^a22 —, —NR ^{a22 CO—} , —SO ₂ —, —CS—, —OCO— or —COO—,
L ² is a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. A group in which v hydrogen atoms are removed from or a group in which v hydrogen atoms are removed from a heterocyclic group having 2 to 20 carbon atoms,
When the group represented by L ² has an alkylene moiety, the alkylene moiety is —O—, —S—, ^—COO— , ^—OCO— , —NR ^a22 —, —NR ^{a22 COO—} , —OCONR ^a22 —. , -SCO-, -COS-, -OCS- or -CSO- may be interrupted 1 to 5 times, and the alkylene moiety may be branched or cyclic,
R ^a6 represents OR ^a41 , SR ^a41 , CONR ^a42 R ^a43 , NR ^a42 COR ^a43 , OCOR ^a41 , COOR ^a41 , SCOR ^a41 , OCSR ^a41 , COSR ^a41 , CSOR ^a41 , CN or a halogen atom,
R ^a41 , R ^a42 and R ^a43 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and R ^a41 , R ^{When the} group represented by ^a42 or R ^a43 has an alkyl moiety, the alkyl moiety may be ^branched or cyclic, and R ^a42 and R ^a43 together form a ring. It may be formed. In the present specification, “R ^a12 and R ^a13 and R ^a22 and R ^a23 are combined to form a ring” means “R ^a12 and R ^a13 and R ^a22 and R ^a23 are each combined. A nitrogen atom, a carbon atom or an oxygen atom connected to each other.
v represents an integer of 1 to 3. )
Represents a group represented by ]

R ^a11 , R ^a12 , R ^a13 , R ^a21 , R ^a22 , R ^a23 , R ^a24 , R ^a31 , R ^a32 , R ^a33 and R ^a34 in formula (1), and R ^a22 , R in formula (2) ^Examples of the alkyl group having 1 to 20 carbon atoms representing ^a41 , ^Ra42 and ^Ra43 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. , Pentyl, isopentyl, t-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl Group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group and the like.

R ^a11 , R ^a12 , R ^a13 , R ^a21 , R ^a22 , R ^a23 , R ^a24 , R ^a31 , R ^a32 , R ^a33 and R ^a34 in formula (1), and R ^a22 , R in formula (2) ^Examples of the aryl group having 6 to 30 carbon atoms representing ^a41 , ^Ra42 , and ^Ra43 include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the above alkyl group. One or more substituted phenyl group, biphenylyl group, naphthyl group, anthryl group and the like can be mentioned.

R ^a11 , R ^a12 , R ^a13 , R ^a21 , R ^a22 , R ^a23 , R ^a24 , R ^a31 , R ^a32 , R ^a33 and R ^a34 in formula (1), and R ^a22 , R in formula (2) ^{Examples of} the C ^7-30 aralkyl group representing a ⁴¹ , R ^a42 , and R ^a43 include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenylethyl group, and the like.

^Examples of the heterocyclic group having 2 to 20 carbon atoms representing R ^a11 , R ^a12 , R ^a13 , R ^a21 , R ^a22 , R ^a23 and R ^a24 in the formula (1) include a pyridyl group, a pyrimidyl group, and a furyl group. , Thienyl group, tetrahydrofuryl group, dioxolanyl group, benzoxazol-2-yl group, tetrahydropyranyl group, pyrrolidyl group, imidazolidyl group, pyrazolidyl group, thiazolidyl group, isothiazolidyl group, isoxazolidyl group, isoxazolidyl group, piperidyl group , A piperazyl group, a morpholinyl group, and the like, preferably a 5- to 7-membered heterocyclic ring.

R ^a12 and R ^a13 , R ^a22 and R ^a23 in formula (1), and R ^a42 and R ^{a43 in} formula (2) can be formed together, and R ^a31 , R ^a32 , R ^a33 Examples of the ring that R ^a34 can form together with the adjacent benzene ring include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring. , Preferably a 5- to 7-membered ring.

L ² in formula (2) is a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, A group obtained by removing v hydrogen atoms from a 7-30 aralkyl group or a group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms.

  Examples of the group in which v hydrogen atoms are removed from an alkyl group having 1 to 20 carbon atoms include, for example, when v is 1, a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, and a 1-methylpropylene group. 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 4-methylbutylene group, 2,4 -Dimethylbutylene group, 1,3-dimethylbutylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, ethane-1,1- Examples thereof include alkylene groups such as a diyl group and a propane-2,2-diyl group.

  Examples of the group in which v hydrogen atoms are removed from an aryl group having 6 to 30 carbon atoms include, when v is 1, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,6-naphthylene group, 1,4-naphthylene group, 2,5-dimethyl-1,4-phenylene group, diphenylmethane-4,4′-diyl group, 2,2-diphenylpropane-4,4′-diyl Groups, arylene groups such as diphenylsulfide-4,4′-diyl group, diphenylsulfone-4,4′-diyl group, and the like.

［式（ａ）及び（ｂ）中、Ｌ^３及びＬ^５は、炭素数１〜１０のアルキレン基を表し、Ｌ^４及びＬ^６は、単結合又は炭素数１〜１０のアルキレン基を表す。］
炭素数１〜１０のアルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、メチルエチレン基、ブチレン基、１−メチルプロピレン基、２−メチルプロピレン基、１，２−ジメチルプロピレン基、１，３−ジメチルプロピレン基、１−メチルブチレン基、２−メチルブチレン基、３−メチルブチレン基、４−メチルブチレン基、２，４−ジメチルブチレン基、１，３−ジメチルブチレン基、ペンチレン基、へキシレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基等が挙げられる。 Examples of the group in which v hydrogen atoms are removed from an aralkyl group having 7 to 30 carbon atoms include, for example, when v is 1, a group represented by the formula (a) and a group represented by the formula (b). Can be mentioned.

[In Formulas (a) and (b), L ³ and L ⁵ represent an alkylene group having 1 to 10 carbon atoms, and L ⁴ and L ⁶ represent a single bond or an alkylene group having 1 to 10 carbon atoms. ]
Examples of the alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, propylene group, methylethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1 , 3-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 4-methylbutylene group, 2,4-dimethylbutylene group, 1,3-dimethylbutylene group, pentylene group, Examples include a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group.

  Examples of the group in which v hydrogen atoms are removed from a heterocyclic group having 2 to 20 carbon atoms include, for example, when v is 1, 2,5-pyridinediyl group, 2,6-pyridinediyl group, 2,5- Pyrimidinediyl group, 2,5-thiophenediyl group, 3,4-tetrahydrofurandiyl group, 2,5-tetrahydrofurandiyl group, 2,5-furandiyl group, 3,4-thiazoldiyl group, 2,5-benzofurandyl And divalent heterocyclic groups such as 2,5-benzothiophenediyl group, N-methylindole-2,5-diyl group, 2,5-benzothiazolediyl group, 2,5-benzoxazolediyl group It is done.

R ^a3 and R ^a4 in formula (1), a halogen atom representing R ^a6 in formula (2), and R ^a11 , R ^a12 , R ^a13 , R ^a21 , R ^a22 and R ^{a23 in} formula (1) are Examples of the halogen atom that may be present as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When the group represented by R ^a11 , R ^a12 , R ^a13 , R ^a21 , R ^a22 or R ^a23 in formula (1) or the group represented by L ² in formula (2) has an alkylene moiety, The alkylene moiety is —O—, —S—, ^—COO— , ^—OCO— , —NR ^a24 —, —NR ^{a24 CO—} , —NR ^{a24 COO—} , —OCONR ^a24 —, —SCO—, —COS—. , -OCS- or -CSO- may be interrupted 1 to 5 times, and the binding group interrupted at this time may be one or two or more groups. It may be interrupted continuously.
^{R a11} in equation ^{(1), R a12, R} a13, R a21, R a22, R a23, R a31, R a32, groups represented by ^{R a33} or ^{R a34} or in formula (2), ^{R a41} , R ^a42 or R ^a43 has an alkyl moiety, the alkyl moiety may be ^branched or cyclic.
Moreover, when the group represented by L ² in Formula (2) has an alkylene moiety, the alkylene moiety may be branched or cyclic.

［式（３）中、Ｌ’は、硫黄原子又はＮＲ^ａ50を表し、Ｒ^ａ50は、直鎖状、分枝鎖状又は環状の炭素数１〜２０のアルキル基を表し、Ｒ^ａ1、Ｒ^ａ2、Ｒ^ａ3、Ｒ^ａ4、Ｒ^ａ5、ｓ及びｔは、上記と同じ意味を表す。］
で表される化合物が好ましい。 Among the compounds (1), the formula (3):

[In the formula (3), L ′ represents a sulfur atom or NR ^a50 , R ^a50 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, R ^a1 , R ^a2 , R ^a3 , R ^a4 , R ^a5 , s and t have the same meaning as described above. ]
The compound represented by these is preferable.

［式（４）中、Ｒ^ａ51及びＲ^ａ52は、それぞれ独立に、炭素数１〜２０のアルキル基を表し、Ｒ^ａ53は、ヒドロキシ基、カルボキシ基又は式（５）

（式（５）中、Ｌ¹¹は、−Ｏ−又は＊−ＯＣＯ−を表し、＊はＬ¹²との結合手を表し、Ｌ¹²は、炭素数１〜２０のアルキレン基を表し、該アルキレン基は、１〜３個の−Ｏ−により中断されていてもよく、Ｒ^ａ54は、ＯＲ^ａ55又はＣＯＯＲ^ａ55を表し、Ｒ^ａ55は、水素原子又は炭素数１〜６のアルキル基を表す。）
で表される基を表す。］
で表される化合物がより好ましい。
化合物（１）がこれらの化合物であると、化合物の製造が容易であり、さらに該化合物を含む感光性樹脂組成物から高感度でパターンを製造することができる。 Furthermore, Formula (4):

[Equation (4), ^{R a51} and ^{R a52} each independently represent an alkyl group having 1 to 20 carbon atoms, ^{R a53} is a hydroxy group, a carboxy group, or the formula (5)

(In the formula (5), L ¹¹ represents -O- or * -OCO-, * represents a bond to L ^12, L ¹² represents an alkylene group having 1 to 20 carbon atoms, said alkylene The group may be interrupted by 1 to 3 —O—, R ^a54 represents OR ^a55 or COOR ^a55 , and R ^a55 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Represents a group represented by ]
The compound represented by these is more preferable.
When the compound (1) is any of these compounds, it is easy to produce the compound, and a pattern can be produced with high sensitivity from the photosensitive resin composition containing the compound.

Carbon number of the alkyl group representing R ^a51 and R ^a52 is preferably 1 to 10, more preferably 1 to 4.
R ^a53 is preferably a group represented by Formula (5).
The number of carbon atoms of the alkylene group representing L ¹² is preferably 1 to 10, more preferably 1 to 4.
R ^a54 is preferably a hydroxy group or a carboxy group, more preferably a hydroxy group.

  Examples of the compound (1) include compounds represented by the following formula. When these compounds are used, when a pattern is produced, there is a tendency that the generation of peeled pieces derived from the colored photosensitive resin composition is reduced in the developer after development. Among these, compound no. 2, Compound No. 26, Compound No. 44, compound no. 45 and compound no. 46 is preferred.

  Although the manufacturing method of compound (1) is not specifically limited, For example, it can manufacture by the method of Unexamined-Japanese-Patent No. 2011-132215.

  Content of compound (I) becomes like this. Preferably it is 30-100 mass% with respect to the total amount of a polymerization initiator (D), More preferably, it is 50-100 mass%. When the content of the compound (I) is in the above range, when a pattern is produced, there is a tendency that a peeled piece generated from the colored photosensitive resin composition is less generated in the developer after development.

The colored photosensitive resin composition of the present invention may contain a polymerization initiator different from the compound (I) as the polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound that initiates polymerization by the action of light or heat, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include biimidazole compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and oxime compounds. Moreover, you may use the light and / or thermal cationic polymerization initiator (For example, what is comprised from the onium cation and the anion derived from a Lewis acid) described in Unexamined-Japanese-Patent No. 2008-181087. Among these, at least one selected from the group consisting of a biimidazole compound, an alkylphenone compound, and an oxime compound is preferable, and two or more types selected from the group consisting of a biimidazole compound, an alkylphenone compound, and an oxime compound are preferable. More preferred. These polymerization initiators are particularly preferred because they tend to be highly sensitive.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Nyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

  The alkylphenone compound is a compound having α-hydroxyalkylphenone, α-alkoxyalkylphenone or α- (N-substituted amino) alkylphenone as a partial structure, specifically, diethoxyacetophenone, 2-hydroxy -2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 2-hydroxy-1 -{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Ruamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-methylbenzyl) -2 -Dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-ethylbenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-butylbenzyl) -2-dimethylamino- 1- (4-morpholinophenyl) butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinov Nyl) butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholino) Phenyl) butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-Bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-methoxybenzyl) 2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methoxybenzyl) -2 -Dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-methyl-4) -Bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer, 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2- Methylphenyl) ete Le] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropan-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H -Carbazol-3-yl] ethane-1-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used.

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) described later.
Moreover, as a polymerization initiator having a group capable of causing chain transfer, a polymerization initiator described in JP-T-2002-544205 may be used.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 5 to 25 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator (D) is in the above range, a pattern can be formed with high sensitivity, and the resulting pattern tends to be excellent in solvent resistance, mechanical strength, and surface smoothness.

  The colored photosensitive resin composition of the present invention may further contain a polymerization initiation assistant (D1) together with the polymerization initiator (D) described above. The polymerization initiation assistant (D1) is used in combination with the polymerization initiator (D), and is a compound or sensitizer used for accelerating the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. . Examples of the polymerization initiation assistant (D1) include thioxanthone compounds, thiazoline compounds, alkoxyanthracene compounds, amine compounds, and carboxylic acid compounds. By combining these with the polymerization initiator (D), a pattern can be obtained with high sensitivity.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  Examples of the thiazoline compound include compounds represented by formulas (III-1) to (III-3), and compounds described in JP-A-2008-65319.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, compounds described in JP-A-2009-139932, and the like can be mentioned.

  Examples of amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylamino. Of 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name; Michler's ketone), 4,4′-bis (diethylamino) benzophenone Such aromatic amine compounds are mentioned.

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Aromatic heteroacetic acids such as phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

  When the polymerization initiation assistant (D1) is included, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 1 to 20 parts by mass. Moreover, Preferably it is 20-100 mass parts with respect to 100 mass parts of content of a polymerization initiator (D), More preferably, it is 30-80 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a pattern can be formed with high sensitivity, and the resulting pattern tends to be excellent in solvent resistance, mechanical strength, and surface smoothness.

  Moreover, the colored photosensitive resin composition of this invention may contain the polyfunctional thiol compound (T) further. The polyfunctional thiol compound (T) refers to a compound having two or more —SH in the molecule. In particular, when a compound having two or more —SH bonded to a carbon atom derived from an aliphatic hydrocarbon group is used, the sensitivity of the colored photosensitive resin composition of the present invention tends to increase.

  Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3- Sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), Trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydro Shiechirutorisu (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

  The content of the polyfunctional thiol compound (T) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass with respect to 100 parts by mass of the polymerization initiator (D). When the content of the polyfunctional thiol compound (T) is in the above range, the sensitivity of the photosensitive resin composition is increased and the developability tends to be favorable, which is preferable.

  The colored photosensitive resin composition of the present invention preferably contains a solvent (E). A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), ketones other than ester solvents A solvent (solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, or the like can be selected and used.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Of the above solvents, organic solvents having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm are preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3- Ethyl ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethyl Formamide is more preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, lactic acid ester Le, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate is more preferred.

  Content of the solvent (E) in a colored photosensitive resin composition becomes like this. Preferably it is 70-95 mass% with respect to a colored photosensitive resin composition, More preferably, it is 75-92 mass%. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

  The colored photosensitive resin composition of the present invention may contain a surfactant (F). Examples of the surfactant include a silicone surfactant, a fluorine surfactant, a silicone surfactant having a fluorine atom, and the like.

Examples of the silicone surfactant include surfactants having a siloxane bond.
Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan GK) Manufactured) and the like.

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain.
Specifically, Florinart (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183 (DIC) ), Ftop (registered trademark) EF301, EF303, EF351, EF351, EF352 (manufactured by Mitsubishi Materials Denkasei), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass) And E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned. Preferably, MegaFac (registered trademark) F475 is used.

  The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.000% by mass or more based on the total amount of the colored photosensitive resin composition. It is 1 mass% or less, More preferably, it is 0.01 mass% or more and 0.05 mass% or less. When the content of the surfactant (F) is in the above range, a coating film with high flatness can be obtained. This content does not include the pigment dispersant described above.

  Various additions such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, and the like are added to the colored photosensitive resin composition of the present invention as necessary. An agent may be included.

The colored photosensitive resin composition of the present invention can be prepared, for example, as follows. When the colorant (A) contains the pigment (A2), the pigment (A2) is mixed with the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. . Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. In the obtained pigment dispersion, the dye (A1), the rest of the resin (B), the polymerizable compound (C), the polymerization initiator (D), the rest of the solvent (E) and other used as necessary By adding and mixing the components so as to have a predetermined content, a desired colored photosensitive resin composition can be obtained.
When the colorant (A) consists only of the dye (A1), the dye (A1), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the solvent (E), and the solvent are used as necessary. The desired colored photosensitive resin composition can be obtained by adding and mixing other components so as to have a predetermined content.
In any of the above cases, the dye (A1), the resin (B), the polymerizable compound (C), the polymerization initiator (D), etc. may be dissolved in the solvent (E) in advance and then mixed.
The mixed colored photosensitive resin composition is preferably filtered with a 0.1 to 10 μm filter.

Examples of a method for forming a color filter pattern using the colored photosensitive resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. In the photolithographic method, the colored photosensitive resin composition is applied to a substrate, a volatile component such as a solvent is removed (dried) to form a colored layer, and the colored layer is exposed through a photomask and developed. Is the method. In the photolithographic method, a coating film may be formed by not using a photomask and / or not developing during exposure.
The film thickness of the pattern to be produced is not particularly limited and can be appropriately adjusted depending on the material used, application, etc., preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm, and still more preferably 0.5 to 6 μm.

As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.
Examples of the coating method include spin coating, slit coating, and slit-and-spin coating.

  As a method of forming each color pixel by the photolithography method, a known or commonly used method can be used. For example, it can be produced as follows.

The colored photosensitive resin composition is applied onto a substrate, and volatile components such as a solvent are removed by drying by heating (pre-baking) and / or drying under reduced pressure to obtain a smooth coating film.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coating film after drying is not specifically limited, It can adjust suitably with the material to be used, a use, etc., for example, is 0.1-20 micrometers, Preferably it is 0.5-6 micrometers.

After drying, the coating film is exposed through a photomask for forming a target pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended application is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
At the time of exposure, it is preferable to use an apparatus such as a mask aligner or a stepper because the entire exposed surface can be irradiated with parallel rays uniformly or the mask and the substrate can be accurately aligned.

After exposure, a pattern can be obtained by contacting a developing solution to dissolve a predetermined portion, for example, an unexposed portion, and developing. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide and the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.
Furthermore, you may post-bake as needed. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 0.5 to 10 minutes, and more preferably 1 to 5 minutes.

  According to the present invention, it is possible to provide a colored photosensitive resin composition capable of producing a color filter having particularly excellent brightness. The color filter is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, etc.), electronic paper, a solid-state image sensor, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部を乳酸エチル７０部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗが９．１×１０^３、分子量分布が２．１、固形分が２６％、固形分酸価が１２４ｍｇ−ＫＯＨ／ｇの樹脂Ｂ１溶液を得た。樹脂Ｂ１は、以下の構造単位を有する。

Synthesis example 1
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, 400 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 45 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound is mixed at a molar ratio of 50:50.) 230 parts are dissolved in 300 parts of ethyl lactate to prepare a solution, and this solution is heated to 70 ° C. over 4 hours using a dropping funnel. It was dripped in the flask kept warm.

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 70 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the temperature is kept at 70 ° C. for 4 hours, and then cooled to room temperature, the weight average molecular weight Mw is 9.1 × 10 ³ , the molecular weight distribution is 2.1, the solid content is A resin B1 solution having 26% solid acid value of 124 mg-KOH / g was obtained. Resin B1 has the following structural units.

Synthesis example 2
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 220 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 84 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) 336 parts in a molar ratio of 50:50) was dissolved in 140 parts of ethyl lactate to prepare a solution, and this solution was kept at 70 ° C. for 4 hours using a dropping funnel. The solution was dropped into the flask. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After dropping of the solution of the polymerization initiator is completed, the temperature is kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 8.0 × 10 ³ , the molecular weight distribution is 2.5, and the solid content is A resin B2 solution having a 48% solution acid value of 50 mg-KOH / g was obtained. The solid content acid value calculated from the solid content and the solution acid value is 104 mg-KOH / g. Resin B2 has the following structural units.

Synthesis example 3
500 parts by mass of propylene glycol monomethyl ether was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Then, after heating the solution in a flask to 100 degreeC, the mixture which consists of 215 mass parts of benzyl methacrylate, 67 mass parts of methacrylic acid, 1.5 mass parts of azobisisobutyronitrile, and 191 mass parts of propylene glycol monomethyl ethers. The mixture was added dropwise to the flask using a dropping funnel over 2 hours. After completion of the addition, the mixture was further stirred at 100 ° C. for 2.5 hours, the weight average molecular weight Mw was 1.1 × 10 ⁴ , the solid content was 29%, the solid content was A resin B3 solution having a partial acid value of 156 mg-KOH / g was obtained. Resin B3 has the following structural units.

The polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resins B1 to B3 were measured using the GPC method under the following conditions.
Apparatus: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector: RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Synthesis example 4
In a flask equipped with a condenser and a stirrer, a mixture of the compound represented by the formula (A1-1a) and the compound represented by the formula (A1-1b) (manufactured by Chugai Kasei Co., Ltd., trade name Chugai Aminol Fast Pink R) was added. Part, 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added dropwise and 10.9 parts of thionyl chloride was added dropwise while maintaining at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and the compound represented by dye A1 (formula (A1-1-1) to formula (A1-1-8)). 11.3 parts of a mixture were obtained.

Synthesis example 5
200 parts of water was added to 10.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), and then adjusted to pH 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 11.1 parts of sodium nitrite was added and stirred for 30 minutes. After adding 39.0 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 10.1 parts of amidosulfuric acid in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  14.0 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-2), 125 parts of water and 25. N-methylpyrrolidone. After adding 0 parts, the solution was adjusted to pH 8-9 with 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 21.4 parts (yield 87%) of the compound represented by the formula (d-3).

Compound (d-3) 0.35 g was dissolved in N, N-dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, cell length is 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λmax = 433 nm.

  Into a flask equipped with a condenser and a stirrer, 5.0 parts of compound (d-3), 35 parts of acetonitrile and 1.6 parts of N, N-dimethylformamide were added, while maintaining at 20 ° C. or lower with stirring. 2.4 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 40 ° C., the reaction was continued for 2 hours at the same temperature, and then cooled to 20 ° C. The cooled reaction solution was poured into 150 parts of ice water with stirring and then stirred for 30 minutes. The precipitated yellow crystals were separated by filtration, washed well with tap water, and dried at room temperature for 1 hour. Prepare a flask equipped with a condenser and a stirrer separately, add 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone, and adjust in advance while maintaining the temperature at 20 ° C. or lower with stirring. The yellow crystals obtained were added over 1 hour. After adding the yellow solid, the liquid temperature was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After adding 40 parts of methanol to the reaction solution and stirring, this mixed solution was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 3.9 parts (yield 69%) of the compound represented by the formula (III-3).

Compound (III-3) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.3 (arbitrary unit) at λmax = 431 nm.

The following reaction was performed in a nitrogen atmosphere. After adding 4.0 parts of N-methylpyrrolidone to 2.0 parts of the compound (III-3), the reaction solution was prepared by stirring for 30 minutes. While stirring the reaction solution at room temperature, 0.1 part of sebacic acid chloride was added dropwise. After completion of dropping, the mixture was further stirred for 8 hours. After pouring the reaction solution into 300 parts of water, 80 parts of ethyl acetate was added and stirred for 30 minutes. The organic phase was separated using a separatory funnel, and further washed with 500 parts of water, 500 parts of a 10% aqueous sodium carbonate solution, 500 parts of an aqueous 10% acetic acid solution, and 500 parts of ion-exchanged water. The separated organic phase was evaporated to obtain 2.0 parts of a compound represented by the formula (4-5). Yield 85%. This compound is sometimes referred to as Dye A2.

The structure of the compound represented by formula (4-5) was determined by mass spectrometry. As the mass spectrometer, JMS-700 (manufactured by JEOL Ltd.) was used.
Mass spectrometry: ionization mode = FD +: m / z = 1200

0.35 g of the compound represented by formula (4-5) is dissolved in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which is diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g). / L), a spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound showed an absorbance of 2.2 (arbitrary unit) at λmax = 431 nm.

The compound represented by the formula (1A) used in the following examples was produced by the method described in JP2011-132215A.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）１５質量部をプロピレングリコールモノメチルエーテルアセテート２２５質量部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗ６．８×１０^３、固形分２６．７質量％、溶液酸価３１ｍｇ−ＫＯＨ／ｇの樹脂Ｂ４溶液を得た。樹脂Ｂ４は、下記の構造単位を有する。

Synthesis Example 6
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel to form a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate was added and stirred to 70 ° C. Heated. Next, 8 parts of acrylic acid, 70 parts of cyclohexylmaleimide, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and formula (II- The compound represented by 1) is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving 32 parts by mass in 140 parts by mass of propylene glycol monomethyl ether acetate, and the solution is added using a dropping funnel. Then, the solution was dropped into a flask kept at 70 ° C. over 4 hours.

On the other hand, a solution obtained by dissolving 15 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of propylene glycol monomethyl ether acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw 6.8 × 10 ³ , the solid content 26.7% by mass, and the solution acid value 31 mg A resin B4 solution of -KOH / g was obtained. Resin B4 has the following structural units.

実施例及び比較例
表１に示す組成となるように、各成分を混合して、着色感光性樹脂組成物を得た。 Synthesis example 7
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel to form a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate was added and stirred to 70 ° C. Heated. Subsequently, 57 parts by mass of acrylic acid, 83 parts of vinyl toluene, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and formula (II) The compound represented by -1) is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving 238 parts by mass in 140 parts by mass of propylene glycol monomethyl ether acetate, and the solution is added to the dropping funnel. It was dripped in the flask kept at 70 degreeC over 4 hours using it. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of propylene glycol monomethyl ether acetate was added to a flask using another dropping funnel over 4 hours. It was dripped in. After completion of dropping of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours and then cooled to room temperature. The weight average molecular weight Mw was 1.04 × 10 ⁴ , solid content 37.4% by mass, solid content A resin B5 solution having a partial acid value of 112 mg-KOH / g was obtained. Resin B5 has the following structural units.

Examples and Comparative Examples Each component was mixed so as to have the composition shown in Table 1 to obtain a colored photosensitive resin composition.

[Preparation of Pigment Dispersion Liquid (A2-1)]
Colorant: C.I. I. Pigment Blue 15: 6 (pigment) 11.4 parts Acrylic pigment dispersant 4.5 parts Solvent: Propylene glycol monomethyl ether acetate 84.2 parts are mixed, and the pigment is sufficiently dispersed by using a bead mill, whereby pigment is obtained. A dispersion (A2-1) was obtained.

[Preparation of pigment dispersion (A2-2)]
Colorant: C.I. I. Pigment Green 58 (pigment) 13.6 parts Acrylic pigment dispersant 2.8 parts Solvent: Propylene glycol monomethyl ether acetate 83.6 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, whereby a pigment dispersion is obtained. (A2-2) was obtained.

[Preparation of pigment dispersion A2-3]
C. I. Pigment Yellow 138 15.0 parts Acrylic pigment dispersant 4.5 parts Propylene glycol monomethyl ether acetate 76.0 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, whereby a pigment dispersion (A2-3) Got.

Example 1
[Preparation of colored photosensitive resin composition 1]
Pigment dispersion (A2-1) 16.4 parts Colorant: Dye A1 0.6 parts Resin: Resin B1 solution 7.5 parts Resin: Resin B3 solution 5.4 parts Polymerizable compound: Dipentaerythritol hexaacrylate
(Kayarad DPHA; manufactured by Nippon Kayaku Co., Ltd.) 4.4 parts Polymerization initiator: compound represented by formula (1A) 1.0 part Polymerization initiator; 2-methyl-2-morpholino-1- (4- Methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF) 0.5 parts Polymerization initiation aid: 0.4 parts of 2,4-diethylthioxanthone
(Kayacure DETX; manufactured by Nippon Kayaku Co., Ltd.)
Solvent: 4.2 parts of propylene glycol monomethyl ether Solvent: 59.6 parts of ethyl 3-ethoxypropionate were mixed to obtain a colored photosensitive resin composition 1.

Example 2
[Preparation of colored photosensitive resin composition 2]
Pigment dispersion (A2-1) 35.3 parts Colorant: Dye A1 0.2 parts Resin: Resin B1 solution 5.3 parts Resin: Resin B3 solution 3.8 parts Polymerizable compound: Dipentaerythritol hexaacrylate
(Kayarad DPHA; manufactured by Nippon Kayaku Co., Ltd.) 3.1 parts Polymerization initiator: Compound represented by formula (1A) 0.7 parts Polymerization initiator; 2-methyl-2-morpholino-1- (4- Methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF) 0.3 part Polymerization initiation aid: 0.3 part of 2,4-diethylthioxanthone
(Kayacure DETX; manufactured by Nippon Kayaku Co., Ltd.)
Solvent: 14.2 parts of propylene glycol monomethyl ether Solvent: 36.7 parts of ethyl 3-ethoxypropionate were mixed to obtain colored photosensitive resin composition 2.

Example 3
[Preparation of colored photosensitive resin composition 3]
Pigment dispersion (A2-2) 24.6 parts Colorant: Dye A2 1.1 parts Resin: Resin B1 solution 12.1 parts Resin: Resin B3 solution 7.3 parts Polymerizable compound: Dipentaerythritol hexaacrylate
(Kayarad DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.3 parts Polymerization initiator: Compound represented by formula (1A) 1.3 parts Polymerization initiator; 2-methyl-2-morpholino-1- (4- Methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF) 0.5 part Polymerization initiation aid: 0.3 part of 2,4-diethylthioxanthone
(Kayacure DETX; manufactured by Nippon Kayaku Co., Ltd.)
Solvent: 16.4 parts of cyclohexanone Solvent: 30.9 parts of propylene glycol monomethyl ether acetate were mixed to obtain a colored photosensitive resin composition 3.

Comparative Example 1
Colorant: C.I. I. Pigment Blue 15: 6 20 parts,
A pigment dispersion in which 5 parts of an acrylic pigment dispersant and 142 parts of propylene glycol monomethyl ether acetate are mixed and the pigment is sufficiently dispersed using a bead mill,
Colorant: Dye A1 3.5 parts Resin: Resin B2 (solid content conversion) 31 parts,
Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 31 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound) 9.3 parts,
Solvent: 170 parts of ethyl lactate, and solvent: 255 parts of propylene glycol monomethyl ether,
Were mixed to obtain a colored photosensitive resin composition.

Example 4
[Preparation of colored photosensitive resin composition 4]
Pigment dispersion (A2-2) 24.6 parts Colorant: Dye A2 1.1 parts Resin: Resin B4 solution 19.8 parts Polymerizable compound: Dipentaerythritol hexaacrylate
(Kayarad DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.3 parts Polymerization initiator: Compound represented by formula (1A) 1.3 parts Polymerization initiator; 2-methyl-2-morpholino-1- (4- Methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF) 0.5 part Polymerization initiation aid: 0.3 part of 2,4-diethylthioxanthone
(Kayacure DETX; manufactured by Nippon Kayaku Co., Ltd.)
Solvent: 16.4 parts of cyclohexanone Solvent: 30.5 parts of propylene glycol monomethyl ether acetate were mixed to obtain a colored photosensitive resin composition 4.

Example 5
[Preparation of colored photosensitive resin composition 5]
Pigment dispersion (A2-2) 24.6 parts Colorant: Dye A2 1.1 parts Resin: Resin B5 solution 14.3 parts Polymerizable compound: Dipentaerythritol hexaacrylate
(Kayarad DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.3 parts Polymerization initiator: Compound represented by formula (1A) 1.3 parts Polymerization initiator; 2-methyl-2-morpholino-1- (4- Methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF) 0.5 part Polymerization initiation aid: 0.3 part of 2,4-diethylthioxanthone
(Kayacure DETX; manufactured by Nippon Kayaku Co., Ltd.)
Solvent: 16.4 parts of cyclohexanone Solvent: 36.0 parts of propylene glycol monomethyl ether acetate were mixed to obtain a colored photosensitive resin composition 5.

Comparative Example 2
[Preparation of colored photosensitive resin composition 6]
Pigment dispersion (A2-2) 19.7 parts Pigment dispersion (A2-3) 2.4 parts Resin: Resin B1 solution 11.6 parts Resin: Resin B3 solution 7.0 parts Polymerizable compound: Dipentaerythritol hexa Acrylate
(Kayarad DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.1 parts Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; BASF Corporation) Manufactured by O-acyloxime compound) 1.2 parts Polymerization initiator; 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF) 0.6 parts Polymerization initiation aid: 0.3 parts of 2,4-diethylthioxanthone
(Kayacure DETX; manufactured by Nippon Kayaku Co., Ltd.)
Solvent: 16.4 parts of cyclohexanone Solvent: 35.6 parts of propylene glycol monomethyl ether acetate were mixed to obtain a colored photosensitive resin composition 6.

Comparative Example 2
[Preparation of colored photosensitive resin composition 7]
Pigment dispersion (A2-2) 19.7 parts Pigment dispersion (A2-3) 2.4 parts Resin: Resin B5 solution 13.7 parts Polymerizable compound: Dipentaerythritol hexaacrylate
(Kayarad DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.1 parts Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; BASF Corporation) Manufactured by O-acyloxime compound) 1.2 parts Polymerization initiator; 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF) 0.6 parts Polymerization initiation aid: 0.3 parts of 2,4-diethylthioxanthone
(Kayacure DETX; manufactured by Nippon Kayaku Co., Ltd.)
Solvent: 16.4 parts of cyclohexanone Solvent: 40.5 parts of propylene glycol monomethyl ether acetate were mixed to obtain a colored photosensitive resin composition 7.

[Preparation of pattern]
A colored photosensitive resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the photomask made of quartz glass having a pattern is set to 100 μm, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) , And was irradiated with light at an exposure dose of 150 mJ / cm ² (based on 365 nm). As a photomask, a mask on which a 50 μm line and space pattern was formed was used. After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and 230 ° C. in an oven. And post-baked for 30 minutes to obtain a pattern.

[Observation of peeled piece]
In the production of the pattern, the developer after development was visually observed. In the case where no peeled piece derived from the colored photosensitive resin composition was observed in the developing solution, the mark was “◯”. If a peeled piece derived from the colored photosensitive resin composition is observed in the developer, it is not preferable because it may adhere as a foreign matter on the pattern and cause a defect. The results are shown in Table 1.

[Evaluation of dissolution time]
A colored photosensitive resin composition was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) in the same manner as described above, and then pre-baked at 100 ° C. for 3 minutes. After cooling, an aqueous developer containing 0.12% nonionic surfactant and 2% sodium carbonate was sprayed at 0.05 hPa with a spin developing machine (SD-408R; manufactured by Oshibe) The time until all of the film applied on the surface was dissolved was measured. The results are shown in Table 1.

[Sensitivity evaluation]
As a photomask, a pattern is produced except that a gray scale mask having each light-transmitting portion (the size of the light-transmitting portion is 5 mm × 8 mm) with respect to the transmittance of quartz glass is used. The same operation was performed to obtain a pattern. The board | substrate with which the pattern was formed was observed visually, and the sensitivity was calculated | required from the following formula. The results are shown in Table 1.
Sensitivity (mJ / cm ² ) = T _M (%) × 50 (mJ / cm ² )
Wherein, T _M, of the pattern formed from the transparent portion remaining on the substrate, representing the transmittance of the transparent portion corresponding to the pattern formed from the lowest transmittance transparent portion. ]

[Film thickness measurement]
About the obtained pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 1.

[Chromaticity evaluation]
About the obtained pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinates in the XYZ color system of CIE (Characteristic function of C light source) x, y) and brightness Y were measured. The results are shown in Table 1.

As shown in Table 1, the colored photosensitive resin composition of the present invention containing the compound (1) was confirmed to have no peeled pieces in the developer and to be rapidly dissolved in the developer.
The yield can be improved by manufacturing a display device using a pattern formed of such a colored photosensitive resin composition as a color filter.

  ADVANTAGE OF THE INVENTION According to this invention, when manufacturing a pattern, it becomes possible to provide the colored photosensitive resin composition with few generation | occurrence | production of the peeling piece derived from a colored photosensitive resin composition in the developing solution after image development. By using this pattern, a color filter having particularly excellent brightness can be produced. The color filter can be suitably used for a display device (for example, a liquid crystal display device, an organic EL device, etc.), electronic paper, a solid-state image sensor, and the like.

Claims (3)

Including a colorant, a resin, a polymerizable compound and a polymerization initiator,
The colorant comprises a xanthene dye and a pigment;
The mass ratio of pigment to xanthene dye is 97: 3 to 70:30,
The resin is a polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride,
A colored photosensitive resin composition, wherein the polymerization initiator is a polymerization initiator containing a compound represented by the formula (1).

[In Formula (1), R ^a1 and R ^a2 each independently represent R ^a11 , OR ^a11 , COR ^a11 , SR ^a11 , CONR ^a12 R ^a13 or CN;
R ^a11 , R ^a12 and R ^a13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group,
The hydrogen atom of the group represented by R ^a11 , R ^a12 or R ^a13 is OR ^a21 , COR ^a21 , SR ^a21 , NR ^a22 R ^a23 , CONR ^a22 R ^a23 , —NR ^a22 —OR ^a23 , —N (COR ^a22 ) — OCOR ^a23 , —C (═N—OR ^a21 ) —R ^a22 , —C (═N—OCOR ^a21 ) —R ^a22 , CN, halogen atom, or COOR ^a21 ,
R ^a21 , R ^a22 and R ^a23 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an alkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group,
The hydrogen atom of the group represented by R ^a21 , R ^a22 or R ^a23 may be substituted with CN, a halogen atom, a hydroxy group or a carboxy group,
When the group represented by R ^a11 , R ^a12 , R ^a13 , R ^a21 , R ^a22 or R ^a23 has an alkylene moiety, the alkylene moiety is represented by —O—, —S—, —COO—, —OCO—, ^{-NR a24 -, - NR a24 CO} -, - NR a24 COO -, - OCONR a24 -, - SCO -, - COS -, - OCS- or -CSO- by which it may be interrupted 1 to 5 times,
R ^a24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R ^a11 , When the group represented by R ^a12 , R ^a13 , R ^a21 , R ^a22 and R ^a23 has an alkyl moiety, the alkyl moiety may be branched, cyclic, or R ^a12 and R ^a13 and R ^a22 and R ^a23 may be bonded together to form a ring,
R ^a3 and R ^a4 are each independently selected from R ^a11 , OR ^a11 , SR ^a11 , COR ^a11 , CONR ^a12 R ^a13 , NR ^a12 COR ^a11 , OCOR ^a11 , COOR ^a11 , SCOR ^a11 , COSR ^a11 , COSR ^a11 , COSR ^a11, , CN or a halogen atom,
s and t each independently represent an integer of 0 to 4,
L represents an oxygen atom, a sulfur atom, a selenium atom, CR ^a31 R ^a32 , CO, NR ^a33 or PR ^a34 ,
R ^a31 , R ^a32 , R ^a33 and R ^a34 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms,
When the group represented by R ^a31 , R ^a32 , R ^a33 or R ^a34 has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R ^a31 , R ^a32 , R ^a33 and R ^a34 may each independently form a ring together with one of the adjacent benzene rings,
R ^a5 is a hydroxy group, a carboxy group or a formula (2)

(In the formula (2), L ¹ represents —O—, —S—, —NR ^a22 —, —NR ^{a22 CO—} , —SO ₂ —, —CS—, —OCO— or —COO—,
L ² is a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. A group in which v hydrogen atoms are removed from or a group in which v hydrogen atoms are removed from a heterocyclic group having 2 to 20 carbon atoms,
When the group represented by L ² has an alkylene moiety, the alkylene moiety is —O—, —S—, ^—COO— , ^—OCO— , —NR ^a22 —, —NR ^{a22 COO—} , —OCONR ^a22 —. , -SCO-, -COS-, -OCS- or -CSO- may be interrupted 1 to 5 times, and the alkylene moiety may be branched or cyclic,
R ^a6 represents OR ^a41 , SR ^a41 , CONR ^a42 R ^a43 , NR ^a42 COR ^a43 , OCOR ^a41 , COOR ^a41 , SCOR ^a41 , OCSR ^a41 , COSR ^a41 , CSOR ^a41 , CN or a halogen atom,
R ^a41 , R ^a42 and R ^a43 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and R ^a41 , R ^{When the} group represented by ^a42 or R ^a43 has an alkyl moiety, the alkyl moiety may be ^branched or cyclic, and R ^a42 and R ^a43 together form a ring. May be formed,
v represents an integer of 1 to 3. )
Represents a group represented by ]   A color filter formed from the colored photosensitive resin composition according to claim 1.   A display device comprising the color filter according to claim 2.