JP6588254B2 - Colored curable resin composition, color filter, and liquid crystal display device - Google Patents

Description

  The present invention relates to a colored curable resin composition, a color filter, and a liquid crystal display device.

  Colored curable resin compositions are used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As such a colored curable resin composition, a colored curable resin composition containing a blue, green, or red pigment alone or a combination of Pigment Blue 15: 6 and a predetermined dye is known as a colorant ( Patent Documents 1 and 2).

JP 10-31308 A JP 2010-32999 A

However, in the above colored curable resin composition, a part of the colored composition layer after exposure is peeled off at the time of development, whereby foreign matters are formed and the pattern shape may not be good.
Therefore, the present invention has an object to provide a colored curable resin composition that gives a color filter having a good pattern shape, with no foreign matter formed by part of the colored composition layer after exposure being peeled off during development. And

The gist of the present invention is as follows.
[1] Contains a dye (Aa), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the binder resin (B) is composed of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. A structural unit (b1) derived from at least one monomer selected from the group, a structural unit (b2) derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure, and a hydroxy group-containing ( Colored curability characterized by being a copolymer having a structural unit (b3) derived from a (meth) acrylate monomer and a structural unit (b4) derived from a monomer of a dicarbonylimide derivative Resin composition.
[2] The total amount of the hydroxy group-containing (meth) acrylic acid ester monomer and the dicarbonylimide derivative monomer is 25% by mass or more and 90% by mass or less in 100% by mass of all monomers [1. ] The colored curable resin composition of description.
[3] The hydroxy group-containing (meth) acrylic acid ester monomer is a hydroxyalkyl (meth) acrylic acid ester having an alkyl group having 1 to 10 carbon atoms,
The colored curable resin composition according to [1] or [2], wherein the monomer of the dicarbonylimide derivative is an N-substituted maleimide having a hydrocarbon group having 4 to 20 carbon atoms.
[4] The colored curable resin composition according to any one of [1] to [3], further including a pigment (Ab).
[5] The dye (Aa) is derived from an anion of a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen or an anion represented by the formula (A-II) The colored curable resin composition according to any one of [1] to [4], which is a compound comprising a polymer anion having a structural unit and a cation having a dye skeleton.
[In formula (A-II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom.
Y represents a divalent aliphatic hydrocarbon group, an arylene group, or a combination thereof, and the methylene group constituting the aliphatic hydrocarbon group may be replaced by an oxygen atom or a nitrogen atom.
R ⁶¹ represents a hydrogen atom or a methyl group. ]
[6] The colored curable resin composition according to any one of [1] to [5], wherein the dye (Aa) is a compound represented by the formula (AI).
[In the formula (AI), R ^{41 to} R ⁴⁴ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms which may have a substituent. A group in which an oxygen atom is inserted between methylene groups constituting the alkyl group, an aromatic hydrocarbon group which may have a substituent, an aralkyl group or hydrogen which may have a substituent Represents an atom. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom is inserted between methylene groups constituting the alkyl group. May be. R ⁴⁸ and R ⁵² may be bonded to each other to form —NH—, —O—, —S— or —SO ₂ —.
Ring T ¹ represents an aromatic heterocyclic ring which may have a substituent.
[Y] ^m− represents an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen, or an anion represented by the formula (A-II) The polymer anion which has the structural unit derived from is represented.
m represents an arbitrary natural number.
In addition, when two or more cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.
[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ have the same meanings as described above, respectively. ]
[In the formula (A-II), X, Y and R ⁶¹ have the same meanings as described above. ]]
[7] A color filter formed from the colored curable resin composition according to any one of [1] to [6].
[8] A liquid crystal display device comprising the color filter according to [7].

  According to the colored curable resin composition of the present invention, a part of the colored composition layer after exposure is peeled off during development so that no foreign matter is formed, and a color filter having a good pattern shape can be provided.

FIG. 1 is a diagram showing evaluation of a pattern shape after applying a colored curable resin composition to a substrate and forming a pattern.

The colored curable resin composition of the present invention contains a dye (Aa), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the binder resin (B) is an unsaturated carboxylic acid and A structural unit (b1) derived from at least one monomer selected from the group consisting of unsaturated carboxylic acid anhydrides, and a structural unit derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure ( b2), a copolymer having a structural unit (b3) derived from a hydroxy group-containing (meth) acrylic acid ester monomer, and a structural unit (b4) derived from a monomer of a dicarbonylimide derivative. It is characterized by that.
Hereinafter, each component of the dye (Aa), the binder resin (B), the polymerizable compound (C), and the polymerization initiator (D) will be described.

Dye (Aa)
Examples of the dye include azo dyes (for example, monoazo dyes, diazo dyes, triazo dyes, metal complex azo dyes), anthraquinone dyes, indigo dyes, phthalocyanine dyes, pyrazolone dyes, stilbene dyes, carotenoid dyes, thiazole dyes, quinoline dyes, Diarylmethane dye, triarylmethane dye, acridine dye, xanthene dye, azine dye, thiazine dye, oxazine dye, cyanine dye, indamine dye, indophenol dye, naphthalimide dye, perylene dye, naphthoquinone dye, quinoneimine dye, methine dye, Examples include azomethine dyes, squarylium dyes, styryl dyes, coumarin dyes, quinoline dyes, tetraazaporphyrin dyes, nitro dyes, and nitroso dyes, which are soluble in organic solvents. Masui. These dyes can be used alone or in combination of two or more.

  Among them, xanthene dye, triarylmethane dye, anthraquinone dye, tetraazaporphyrin dye, azo dye, cyanine dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye Quinoline dyes and nitro dyes are preferred, xanthene dyes, triarylmethane dyes, coumarin dyes, anthraquinone dyes, and tetraazaporphyrin dyes are more preferred, and xanthene dyes are particularly preferred.

  As the xanthene dye, C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described), 52, 87, 92, 94, 388, C.I. I. Acid Violet 9, 30C. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Examples thereof also include Reactive Red 36 (Rose Bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, and xanthene dyes described in Japanese Patent No. 4492760.

  The xanthene dye is more preferably a compound represented by the following formula (a1-1) (hereinafter also referred to as compound (a1-1)). The compound (a1-1) may be a tautomer thereof.

[In formula (a1-1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a methylene group (—CH ₂ —) contained in the saturated hydrocarbon group, —O—, —CO— or It may be replaced by —NR ¹¹ —. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing a nitrogen atom.
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 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ¹¹ may be the same or different.
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.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH ₂ contained in the saturated hydrocarbon group — May be replaced by —O—, —CO—, —NH— or —NR ⁸ —, wherein R ⁹ and R ¹⁰ are bonded to each other, and a 3- to 10-membered heterocyclic ring containing a nitrogen atom May be formed.
R ¹¹ 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. ]

  Moreover, as a xanthene dye, the compound (henceforth a "compound (a1-2)") represented by a formula (a1-2) is also preferable. The compound (a1-2) may be a tautomer thereof.

[In Formula (a1-2), R ²¹ and R ²² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and are included in the saturated hydrocarbon group of R ²¹ and R ^22. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group is substituted with an alkoxy group having 1 to 3 carbon atoms. And —CH ₂ — contained in the saturated hydrocarbon group of R ²¹ and R ²² may be replaced by —O—, —CO— or —NR ¹¹ —.
R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ²¹ and R ²³ may be combined to form a ring containing a nitrogen atom, and R ²² and R ²⁴ may be combined to form a ring containing a nitrogen atom.
p and q represent the integer of 0-5 mutually independently. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different.
R ¹¹ represents the same meaning as described above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ²¹ and R ²² include those having 1 to 10 carbon atoms among those in R ⁸ .
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include the same groups as those in R ¹ .
As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example.
R ²¹ and R ²² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
R ²³ and R ²⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

  p and q are preferably an integer of 0 to 2, and preferably 1 or 2.

  The triarylmethane dye is preferably a dye containing a compound having a structure in which three aromatic hydrocarbon groups are bonded to one carbon atom. Examples of the triarylmethane dye include C.I. I. Solvent Blue 2, 4, 5, 43, 124; I. Basic Violet 3, 14, 25; C.I. I. And triarylmethane dyes described in Basic Blue 1, 5, 7, 11, 26 and Japanese Patent No. 4492760.

  The coumarin dye is a dye containing a compound having a coumarin skeleton in the molecule. Examples of the coumarin dye include C.I. I. Acid Yellow 227, 250; I. Disperse yellow 82, 184; C.I. I. Solvent Orange 112; C.I. I. Solvent Yellow 160, 172; Coumarin dyes described in Japanese Patent No. 1299948; and the like.

As an anthraquinone dye, C.I. I. Solvent Yellow 117 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 163, 167, 189,
C. I. Solvent orange 77, 86,
C. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,
C. I. Solvent Green 3, 28, 29, 32, 33,
C. I. Acid Red 80,
C. I. Acid Green 25, 27, 28, 41,
C. I. Acid Violet 34,
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112
C. I. Disperse Yellow 51,
C. I. Disperse violet 26, 27,
C. I. Disperse Blue 1, 14, 56, 60,
C. I. Direct Blue 40,
C. I. Modern Red 3, 11,
C. I. Modern Blue 8 etc. are mentioned.

  The tetraazaporphyrin dye is a compound having a tetraazaporphyrin skeleton in the molecule. Further, when the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.

As other dyes, azo dyes, thiazole dyes, oxazine dyes, phthalocyanine dyes, quinophthalone dyes and the like may be used, and known dyes are used.
Examples of the azo dye include C.I. I. Direct yellow (hereinafter, description of CI direct yellow is omitted and only the number is described) 2, 33, 34, 35, 39, 50, 69, 70, 71, 86, 93, 94, 95 98, 102, 109, 129, 136, 141;
C. I. Direct orange 41, 46, 56, 61, 64, 70, 96, 97, 106, 107;
C. I. Direct Red 79, 82, 83, 84, 97, 98, 99, 106, 107, 172, 173, 176, 177, 179, 181, 182, 204, 207, 211, 213, 218, 221, 222, 232, 233, 243, 246, 250;
C. I. Direct violet 47, 52, 54, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 51, 57, 71, 81, 84, 85, 90, 93, 94, 95, 98, 100, 101, 113, 149, 150, 153, 160, 162, 163, 164, 166, 167, 170, 172, 188, 192, 193, 194, 196, 198, 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;
C. I. Direct green 27, 34, 37, 65, 67, 68, 69, 72, 77, 79, 82, etc .;
C. I. Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337;
C. I. Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127;
C. I. Acid Violet 11, 56, 58;
C. I. Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151;
C. I. Acid Brown 2, 4, 13, 248;
C. I. Acid Blue 92, 102, 113, 117, etc .; I. B. Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46: 1, 82; I. C. Basic Orange 2, 24, 25; I. C. basic violet 18; I. Basic yellow 15, 24, 25, 32, 36, 41, 73, 80; I. B. Basic Brown 1; C.I. I. Basic blue 41, 54, 64, 66, 67, 129 etc. are mentioned.

Examples of thiazole dyes include C.I. I. Direct Yellow 54, C.I. I. Basic yellow 1 is mentioned.
Examples of the oxazine dye include C.I. I. Direct Blue 97, 99, 106, 107, 108, 109, 190, 293 and the like can be mentioned.
Examples of the phthalocyanine dye include C.I. I. Direct Blue 86, 87, 189, 199, C.I. I. Acid Blue 249, C.I. I. Basic blue 3 etc. are mentioned.
Examples of the quinophthalone dye include C.I. I. Acid Yellow 3, CI Disperse Yellow 143 and the like. Examples of cyanine dyes include copper phthalocyanine (C.I. 74160).
Examples of quinoneimine dyes include C.I. I. Basic Blue 3, C.I. I. Basic blue 9 etc. are mentioned.
Methine dyes include CI Basic Red 13, 14; CI Basic Orange 21; CI Basic Violet 16, 39; CI Basic Yellow 11, 13, 21, 23, 28, etc. Can be mentioned.
Examples of quinoline dyes include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like.
Nitro dyes include C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
Examples of azine dyes include CI Acid Blue 59,102.
Examples of indigo dyes include CI Acid Blue 74.

  In the dye (Aa), a structural unit derived from an anion of a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen or an anion represented by the formula (A-II) A compound formed from a polymer anion having cation and a cation having a dye skeleton (hereinafter sometimes referred to as compound (AA)) may be included.

  The dye skeleton possessed by the cation constituting the dye includes an azo skeleton, a xanthene skeleton, an azine skeleton, a cyanine skeleton, an acridine skeleton, an anthraquinone skeleton, a squarylium skeleton, etc .; a dye skeleton having an onium structure; a triarylmethane skeleton; Examples thereof include a dye skeleton in which one or more aromatic hydrocarbon rings in the skeleton are aromatic heterocycles. Among them, preferably one or more of the aromatic hydrocarbon rings of the xanthene skeleton introduced with an onium structure, the cyanine skeleton introduced with the onium structure, the squarylium skeleton introduced with the onium structure, the triarylmethane skeleton, and the triarylmethane skeleton are aromatic. A dye skeleton having a heterocyclic ring, and more preferably a dye skeleton having one or more aromatic hydrocarbon rings of a triarylmethane skeleton as an aromatic heterocyclic ring. As the anion, an anion of a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen or a heavy unit having a structural unit derived from an anion represented by the formula (A-II) Examples include a combined anion.

  Specifically, the dye (Aa) is preferably a compound represented by the formula (AI) (hereinafter also referred to as “compound (AI)”).

[In the formula (AI), R ^{41 to} R ⁴⁴ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms which may have a substituent. A group in which an oxygen atom is inserted between methylene groups constituting the alkyl group, an aromatic hydrocarbon group which may have a substituent, an aralkyl group or hydrogen which may have a substituent Represents an atom. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom is inserted between methylene groups constituting the alkyl group. It may be. R ⁴⁸ and R ⁵² may be bonded to each other to form —NH—, —O—, —S—, or —SO ₂ —.
Ring T ¹ represents an aromatic heterocyclic ring which may have a substituent.
[Y] ^m− represents an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen, or an anion represented by the formula (A-II) The polymer anion which has the structural unit derived from is represented.
[In formula (A-II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom.
Y represents a divalent aliphatic hydrocarbon group, an arylene group, or a combination thereof, and the methylene group constituting the aliphatic hydrocarbon group may be replaced by an oxygen atom or a nitrogen atom.
R ⁶¹ represents a hydrogen atom or a methyl group. ]
m represents an arbitrary natural number.
When a plurality of cations represented by the following formula are contained in one molecule, they may be the same structure or different structures.

[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ have the same meanings as described above, respectively. ]]

The aromatic heterocyclic ring of ring T ¹ may be a single ring or a condensed ring. The aromatic heterocycle is preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring. The monocyclic aromatic heterocycle includes, for example, a 5-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring or a thiazole ring; a 5-membered ring not containing a nitrogen atom such as a furan ring or a thiophene ring Ring; 6-membered ring containing nitrogen atom such as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring; and the like, and the aromatic heterocycle of condensed ring includes indole ring, benzimidazole ring, benzothiazole ring, quinoline A condensed ring containing a nitrogen atom such as a ring; a condensed ring containing no nitrogen atom such as a benzofuran ring;
The substituent that the aromatic heterocyclic ring of ring T ¹ may have includes a halogen atom, a cyano group, an optionally substituted alkyl group having 1 to 20 carbon atoms, and a substituent. Examples thereof include an aromatic hydrocarbon group having 6 to 20 carbon atoms and an amino group which may have a substituent.
Among them, the aromatic heterocyclic ring of the ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a 5-membered aromatic heterocyclic ring containing a nitrogen atom.

Ring T ¹ is more preferably a ring represented by the formula (Ab2-x1).

[Ring T ² represents an aromatic heterocyclic ring.
R ⁴⁵ and R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group having 2 to 20 carbon atoms, which constitutes the alkyl group. A group in which an oxygen atom is inserted between methylene groups, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ⁵⁵ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.
k1 represents 0 or 1.
* Represents a bond with a carbocation. ]

Examples of the aromatic heterocycle of the ring T ² include the same rings as the aromatic heterocycle exemplified in the ring T ¹ .
Furthermore, the ring T ¹ is particularly preferably a ring represented by the formula (Ab2-y1).

[R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.
X2 represents an oxygen atom, -NR ⁵⁷ - represents a or sulfur atom.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ⁴⁵ and R ⁴⁶ are as defined above.
* Represents a bond with a carbocation. ]

The ring T ¹ is also preferably a ring represented by the formula (Ab2-x2).

[Ring T ³ represents an aromatic heterocyclic ring having a nitrogen atom.
R ⁵⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.
R ⁵⁹ may have a hydrogen atom, a C 1-20 saturated hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent or a substituent. Represents a good aralkyl group.
k2 represents 0 or 1.
* Represents a bond with a carbocation. ]

The ring T ¹ is more preferably a ring represented by the formula (Ab2-y2).

[R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.
R ⁵⁹ has the same meaning as described above.
* Represents a bond with a carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ^{58 to} R ⁶⁰ may be linear, branched or cyclic. Examples of linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, icosyl, etc. Linear alkyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and the like. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.

The cyclic saturated hydrocarbon group represented by R ^{41 to} R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ^{58 to} R ⁶⁰ may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

The saturated hydrocarbon group of R ^{41 to} R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ^{58 to} R ⁶⁰ may be substituted with a halogen atom or an optionally substituted amino group. Examples of the optionally substituted amino group include an amino group; an alkylamino group such as a dimethylamino group and a diethylamino group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. When the halogen atom is a fluorine atom, the halogen atom is preferably substituted so as to form a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, or a heptafluoropropyl unit.
As a C1-C20 saturated hydrocarbon group which has a substituent, group represented by a following formula is mentioned, for example. In the following formula, * represents a bond with a nitrogen atom.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ^54, carbon atoms of the saturated hydrocarbon group having a straight chain or branched chain exemplified as saturated hydrocarbon groups represented by R ⁴¹ 1-8 The group of is mentioned.
The alkyl group having 1 to 10 carbon atoms represented by R ^57, 1 to 10 carbon atoms of the saturated hydrocarbon group having a straight chain or branched chain exemplified as saturated hydrocarbon group represented by R ⁴¹ Groups.

In the alkyl group represented by R ^{41 to} R ⁵⁴ , an oxygen atom may be inserted between carbon atoms. The preferable carbon number of the alkyl group is 2 to 10, more preferably 2 to 8. When an oxygen atom is inserted, the number of carbon atoms between the terminal and the oxygen atom or between the oxygen atom and the oxygen atom is, for example, 1 to 5, preferably 2 to 3, and more preferably 2 It is. Examples of such a group in which an oxygen atom is inserted between carbon atoms of a saturated hydrocarbon group include an alkoxyalkyl group; or (alkoxyalkoxy) alkyl group, (alkoxyalkoxyalkoxy) alkyl group, and (alkoxyalkoxyalkoxyalkoxy). A polyalkoxyalkyl group such as an alkyl group, (alkoxyalkoxyalkoxyalkoxyalkoxy) alkyl group, (alkoxyalkoxyalkoxyalkoxyalkoxyalkoxy) alkyl group, and the like are included, and the number of repeating alkoxy units is, for example, 1 to 6, preferably 1. -4, more preferably 1-2. More preferred specific examples include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

In addition, the aromatic hydrocarbon group which may have a substituent represented by R ^{41 to} R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ^{58 to} R ⁶⁰ preferably has 6 to 20 carbon atoms. More preferably, it has 6 to 15 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, preferably a phenyl group, a naphthyl group, a tolyl group, A xylyl group, particularly preferably a phenyl group. The aromatic hydrocarbon group may have one or more substituents, and examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom and bromine atom; chloromethyl group, A haloalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; a sulfamoyl group; an alkylsulfonyl having 1 to 6 carbon atoms such as a methylsulfonyl group Group; an alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; and the like. Specific examples of the aromatic hydrocarbon group which may be substituted include groups represented by the following formulas. In the following formula, * represents a bond with a nitrogen atom.

Examples of the aralkyl group which may have a substituent represented by R ^{41 to} R ⁴⁶ and R ⁵⁹ include the groups described as the aromatic hydrocarbon group described above and a carbon number of 1 such as a methylene group, an ethylene group and a propylene group. And a group to which 5 alkanediyl groups are bonded.

A ring formed by combining R ⁴¹ and R ⁴² with the nitrogen atom to which they are bonded, a ring formed by combining R ⁴³ and R ⁴⁴ with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ⁴⁶ Examples of the ring formed together with the nitrogen atom to which they are bonded include nitrogen-containing non-aromatic 4- to 7-membered rings such as pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring, preferably pyrrolidine ring, piperidine ring 4-7 membered ring which has only one nitrogen atom as a hetero atom, such as.

Among these, as R ^{41 to} R ⁴⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁸ and R ⁵⁹ , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent is preferable. It is more preferable that they are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group represented by the following formula. R ⁵⁵ is more preferably an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

R ^{45 to} R ⁴⁶ each independently has a saturated hydrocarbon group having 1 to 20 carbon atoms, a group in which an oxygen atom is inserted between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or a substituent. It is preferably an aromatic hydrocarbon group that may be present, or R ⁴⁵ and R ⁴⁶ are bonded to form a ring together with the nitrogen atom to which they are bonded. In a more preferred embodiment, R ^{45 to} R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an aromatic hydrocarbon group represented by the following formula: Alternatively, R ⁴⁵ and R ⁴⁶ are bonded to form a 4- to 7-membered ring having only one nitrogen atom as a hetero atom. In the following formula, * represents a bond with a nitrogen atom.

Examples of the group in which an oxygen atom is inserted between the carbon atoms of the alkyl group having 1 to 8 carbon atoms and the alkyl group having 2 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ include R ^{41 to} R. ^The group which selected the thing of carbon number 8 or less from ⁴⁶ corresponding groups can be illustrated, More preferably, the group represented by a following formula is mentioned. In the following formula, * represents a bond with a carbon atom.

R ^{47 to} R ⁵⁴ are preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms from the viewpoint of ease of synthesis, and each independently represents a hydrogen atom or a methyl group. More preferably, they are a fluorine atom or a chlorine atom.

  Examples of the cation moiety of formula (Ab2) include cation 1 to cation 14 represented by formula (Ab2-1) as shown in Table 1 below. In the table, * represents a bond.

  In Table 1, Ph1 to Ph9 mean groups represented by the following formulae. In the formula, * represents a bond.

  Examples of the cation moiety of the formula (Ab2) include cations 15 to 18 represented by the formula (Ab2-2) as shown in Table 2 below. In the table, * represents a bond.

  In Table 2, Ph1, Ph10, and Ph11 mean groups represented by the following formulae. In the formula, * represents a bond.

  Among them, as the cation moiety of the formula (Ab2), cation 1 to cation 6 and cation 11 to cation 14 are preferable, cation 1, cation 2, and cation 12 to cation 14 are particularly preferable, and cation 12 is most preferable.

[Y] ^m− may also represent a polymer having a structural unit derived from an anion represented by the formula (A-II) (hereinafter sometimes referred to as “anion (A-II)”).

[In Formula (A-II), X represents an alkyl group having 8 or less carbon atoms in which a part of hydrogen atoms may be substituted with fluorine atoms. Y represents a divalent aliphatic hydrocarbon group, an arylene group, or a combination thereof, and the aliphatic hydrocarbon group and the methylene group constituting the arylene group may be replaced with an oxygen atom or a nitrogen atom. . R ⁶¹ represents a hydrogen atom or a methyl group. ]

In the formula (A-II), X is preferably a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms from the viewpoint of increasing the acidity of the imidic acid. For example, —CF ₃ , —CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₃ , —CF (CF ₃ ) ₂ , —CF ₂ CF ₂ CF ₂ CF ₃ , —CF ₂ CF (CF ₃ ) ₂ , —C (CF ₃ ) _3, etc. -8 halofluoroalkyl groups. Further, the carbon number of X is 2 or more and 8 or less, more preferably 3 or more, and further preferably 4 or more.

The divalent group for Y is preferably a linear or branched alkylene group, an arylene group, or an arylene alkylene group. Y preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Specifically, the linear or branched alkylene group preferably has 1 to 10 carbon atoms, the arylene group preferably has 6 to 20 carbon atoms, and the arylene alkylene group has 7 to 20 carbon atoms. Preferably there is.
The alkylene group may be linear or branched, and examples thereof include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and a butylene group.
Examples of the arylene group include a phenylene group and a naphthylene group.
Examples of the arylene alkylene group include an arylene methylene group, an arylene ethylene group, an arylene propylene group, an arylene butylene group, an arylene pentylene group, and an arylene hexylene group. The arylene alkylene group is preferably bonded to the sulfur atom on the arylene group side.
The methylene group constituting the alkylene group or arylene alkylene group may be replaced with an oxygen atom or a nitrogen atom. Among these, as Y, an arylene group or an arylene alkylene group having 7 to 10 carbon atoms is preferable. Among them, an arylene group, an arylmethylene group, an arylethylene group, an arylpropylene group, an arylenebutylene group, an arylenepentylene group, An arylene hexylene group is more preferred, an arylene group is further preferred, and a phenylene group is particularly preferred.

  Examples of the anionic compound include anionic compounds represented by the following formulas (A-II-1) to (A-II-6).

  These anions (A-II) may be used alone or in combination of two or more.

[Y] ^m− corresponding to the anion is preferably an anion containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus. A compound using such an anion can improve heat resistance and solvent resistance.
[Y] ^m- is preferably an anion of a heteropolyacid or isopolyacid containing tungsten, particularly an anion of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid.

Examples of the anion of heteropolyacid or isopolyacid containing tungsten include Keggin phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^{6 -} , Β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and mixtures thereof.

[Y] ^m− is also preferably an anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus.
Examples of the anion consisting of oxygen and at least one element selected from the group consisting of silicon and phosphorus include SiO ₃ ²⁻ and PO ₄ ³⁻ .

Because of the ease of synthesis and post-treatment, phosphotungstic anions such as Keggin phosphotungstic ion and Dawson phosphotungstic ion; silicotungstic anions such as Keggin silicotungstate ion, [W ₁₀ O ₃₂ ] ^4- A tungsten isopolyacid anion such as Of these, phosphotungstate anions and tungsten isopolyacid anions are particularly preferred.

  As dye (Aa), the compound represented by a following formula is mentioned, for example.

  Especially, it is preferable that a compound (AI) is a compound represented by a formula (Aa2-53).

  The content of the dye (Aa) in the colored curable resin composition is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 60% by mass or less, based on the total amount of the solid content. More preferably, it is 10 mass% or more and 60 mass% or less, Most preferably, it is 15 mass% or more and 50 mass% or less. When the content of the dye (Aa) is within the above range, a desired spectrum and color density can be easily obtained. In addition, in this specification, "the total amount of solid content" means the total amount of the component remove | excluding the solvent from the colored curable resin composition of this invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography and gas chromatography, for example.

The compound represented by the formula (AI) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and still more, in 100% by mass of the dye (Aa). Preferably it is 80 mass% or more, Especially preferably, it is 90 mass% or more, Most preferably, it is 100 mass%.
The dye (preferably xanthene dye) other than the compound (AI) is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass in 100% by mass of the dye (Aa). It is 20 mass% or less, More preferably, it is 1.0 mass% or more and 10 mass% or less.

  Compound (AI) can be produced according to the method described in JP-A-2015-28121.

Colored dispersion In the present invention, a compound comprising an anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus (hereinafter referred to as compound (AA) ) Is preferably mixed with a solvent to prepare a colored dispersion. When a colored curable resin composition is formed by mixing with a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), etc. after making a colored dispersion, the heat resistance when a color filter is formed is obtained. It can be further increased.

Any solvent can be used as long as it can be used as the solvent (E) of the colored curable resin composition. A particularly excellent solvent for the purpose of dispersing the compound (AA) is, for example, an ether ester solvent. More preferably, one hydroxy group of alkylene glycol or polyalkylene glycol is etherified, and the remaining hydroxy group is esterified. Solvents such as 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, diethylene glycol Examples include propylene glycol methyl ether acetate. These may be contained alone or in combination.
The amount of the solvent is usually 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 10 parts by mass with respect to 1 part by mass of the compound (AA).

  In preparing the colored dispersion, it is preferable to use a dispersant. As the dispersant, for example, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic can be used. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.

  The amount of the dispersant is usually 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the compound (AA). It is.

  Moreover, when dye (Aa) other than a compound (AA) is contained in the colored curable resin composition mentioned later, a coloring dispersion liquid is a part of dye (Aa) other than a compound (AA) as needed, or All, preferably all, may be included in advance. The amount of the dye (Aa) other than the compound (AA) in the colored dispersion is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the compound (AA). More preferably, it is 1-5 mass parts.

  The colored dispersion may contain a part or all of the binder resin (B) used in the colored curable resin composition, preferably a part thereof, if necessary. By including the binder resin (B) in advance, the dispersibility when the colored curable resin composition is obtained can be further improved. The solid content conversion amount of the binder resin (B) in the colored dispersion is usually 1 to 300 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 70 parts per 100 parts by weight of the compound (AA). Part by mass.

  In preparing the dispersion, it is preferable to finely disperse using a dispersion apparatus after appropriately adding necessary components. A bead mill device can be used as the dispersing device. The beads used are generally hard beads such as zirconia beads, and the particle size thereof is selected from the range of 0.05 mm or more and 20 mm or less, preferably 0.1 to 10 mm, more preferably. 0.1 to 0.5 mm.

  The content of the dye (Aa) in the colored curable resin composition (when the composition contains a pigment) is usually 1% by mass or more and 45% by mass or less, preferably 2% by mass with respect to the total amount of solids. % To 40% by mass, more preferably 3% to 35% by mass, and particularly preferably 5% to 30% by mass. When the content of the dye (Aa) is within the above range, the desired brightness can be easily obtained.

  The colored curable resin composition of the present invention may further contain a pigment (Ab).

Pigment (Ab)
The pigment is not particularly limited, and a known pigment can be used. For example, pigments classified as pigments in the color index (published by The Society of Dyers and Colorists) can be mentioned, and these can be used alone or in combination of two or more.
Specifically, 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, 129, 137, 138, Yellow pigments such as 139, 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;
C. 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;
Is mentioned. Among them, C.I. I. Pigment Blue 15: 6 is preferable.

  If necessary, the pigment is atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment to the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, 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 particle size is preferably substantially uniform. The pigment can be made into a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by carrying out a dispersion treatment by containing a pigment dispersant. The pigments may be subjected to a dispersion treatment alone, or a plurality of types may be mixed and dispersed.

Examples of the pigment dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples include polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Corporation), EFKA (registered trademark) ) (Manufactured by BASF), Azisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 0 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion with a more uniform dispersion state is obtained.

  When the pigment (Ab) is contained, the content of the pigment (Ab) is preferably 1% by mass or more and 90% by mass or less, more preferably 2% by mass or more and 85% by mass with respect to the total amount of the dye and the pigment. Hereinafter, it is more preferably 5% by mass or more and 80% by mass or less.

Binder resin (B)
The binder resin (B) includes a structural unit (b1) derived from at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, an ethylenically unsaturated bond, and a cyclic ether. A structural unit derived from a monomer having a structure (b2), a structural unit derived from a hydroxy group-containing (meth) acrylic acid ester monomer (b3), and a monomer of a dicarbonylimide derivative. It is a copolymer having the structural unit (b4).
The binder resin (B) of the present invention may contain other structural units as long as it includes the structural units (b1) to (b4). With the binder resin of the present invention, it is possible to improve the pattern shape and reduce the generation of foreign matter.

As at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride constituting the structural unit (b1), acrylic acid, methacrylic acid, crotonic acid, o-, m-, unsaturated monocarboxylic acids such as 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, 1,4-cyclohexenedicarboxylic 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 [2.2.1] bicyclounsaturated compounds containing a carboxy group such as 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- Examples thereof include unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.
In addition, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and other polyvalent carboxylic acid unsaturated mono [(meth) acryloyloxy Alkyl] esters; unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule such as α- (hydroxymethyl) acrylic acid may be used.
Especially, it is preferable that the monomer which comprises a structural unit (b1) is unsaturated monocarboxylic acid, More preferably, they are acrylic acid and methacrylic acid.

  In the present specification, the notation such as “(meth) acrylic acid” and “(meth) acrylate” represents at least one selected from the group consisting of acrylic acid (acrylate) and methacrylic acid (methacrylate).

  A monomer having an ethylenically unsaturated bond and a cyclic ether structure constituting the structural unit (b2) is, for example, an ethylenically unsaturated bond and a C2-C4 cyclic ether structure (for example, an oxirane ring or an oxetane ring). And a polymerizable compound having at least one selected from the group consisting of a tetrahydrofuran ring.

  As the structural unit (b2), for example, a monomer (b2-1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b2-1)”), an oxetanyl group and an ethylenically unsaturated group. Monomer (b2-2) having a saturated bond (hereinafter sometimes referred to as “(b2-2)”), monomer (b2-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as “(b2-2)”) “(B2-3)” in some cases).

  The structural unit (b2-1) includes, for example, a monomer (b2-1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b2- 1-1) ”) and a monomer (b2-1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter referred to as“ (b2-1-2) ”) There are).

  As (b2-1-1), 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) ) Tylene, 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 (b2-1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (I), Formula (I II)) and the like.

[In Formula (I) and Formula (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X ^b1 and X ^b2 represents a single ^{bond, -R b3 -, * - R} b3 -O -, * - R b3 -S- or * -R ^b3 represents a -NH-.
R ^b3 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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and 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 ^b1 and R ^b2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group 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 ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O—, more preferably a single bond, * —CH _2. CH ₂ —O— can be mentioned. * Represents a bond with O.

  Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I-15) A compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferred.

  Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) A compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio thereof [the compound represented by the formula (I): the compound represented by the formula (II)] is: On a molar basis, it is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.

  (B2-2) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (B2-2) includes 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl Examples thereof include oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

  (B2-3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (b2-3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

  The structural unit (b2) is preferably (b2-1) from the viewpoint that the cured film obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b2-1-2) is more preferable in terms of excellent storage stability of the curable resin composition, and a compound represented by the formula (I) and a compound represented by the formula (II) are more preferable. The compound represented by formula (I-1) and the compound represented by formula (II-1) are even more preferred.

  Examples of the hydroxy group-containing (meth) acrylic acid ester monomer constituting the structural unit (b3) include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate, etc. And hydroxy group-containing alkyl (meth) acrylic acid esters.

  The hydroxy group-containing (meth) acrylic acid ester monomer is preferably a hydroxyalkyl (meth) acrylic acid ester having an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably. Is a hydroxy group-containing (meth) acrylic acid ester having an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

  Especially, the monomer which comprises a structural unit (b3) is especially hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 2-hydroxyethyl (meth) acrylate is preferred and most preferred.

  Examples of the monomer of the dicarbonylimide derivative constituting the structural unit (b4) include dicarbonylimide having an aromatic carbon hydrogen group such as N-phenylmaleimide and N-tolylmaleimide, N-cyclohexylmaleimide, and N-cycloheptide. Dicarbonylimide having an alicyclic hydrocarbon group such as ptylmaleimide, N-cyclooctylmaleimide, N-cyclododecylmaleimide, N-benzylmaleimide, dicarbonylimide having an aralkyl group such as N-phenethylmaleimide, N-succinimidyl Dicarbonylimide having a succinimidyl group such as -3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate N-(9-acridinyl) dicarbonyl imide having a condensed heterocyclic group of the maleimide and the like.

The monomer of the dicarbonylimide derivative is preferably an N-substituted maleimide having a hydrocarbon group having 4 to 20 carbon atoms, more preferably an alicyclic hydrocarbon group having 4 to 20 carbon atoms or aromatic carbonization. An N-substituted maleimide having a hydrogen group, an aralkyl group, a succinimidyl group, or a condensed heterocyclic ring.
The number of carbon atoms is more preferably 4 to 16, still more preferably 4 to 12, and particularly preferably 4 to 8.
The hydrogen atom contained in the hydrocarbon group may be substituted with an amino group, an alkoxy group having 1 to 5 carbon atoms, a phenylamino group, a halogen atom, a hydroxy group, or the like.
Among them, the monomer of the dicarbonylimide derivative is more preferably an N-substituted maleimide having an alicyclic hydrocarbon group having 4 to 20 carbon atoms, still more preferably N-cyclohexylmaleimide, N-cycloheptylmaleimide, N -Cyclooctylmaleimide, N-cyclododecylmaleimide, particularly preferably N-cyclohexylmaleimide.

The binder resin (B) of the present invention uses the following monomers in addition to the structural units (b1) to (b4), and may contain other structural units.
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 [2.2 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, etc. Bicyclo unsaturated compounds;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene; vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride Halogenated hydrocarbons such as: vinyl group-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene dienes;

The at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride is preferably 1 to 40% by mass, more preferably 2%, out of 100% by mass of all monomers. It is -35 mass%, More preferably, it is 5-30 mass%.
The monomer having an ethylenically unsaturated bond and a cyclic ether structure is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and still more preferably 5 to 30% by mass in 100% by mass of all monomers. %.
The hydroxy group-containing (meth) acrylic acid ester monomer is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and further preferably 3 to 25% by mass in 100% by mass of all monomers. %.
The monomer of the dicarbonylimide derivative is preferably 25 to 80% by mass, more preferably 35 to 75% by mass, still more preferably 45% by mass or more, and still more preferably 100% by mass of all monomers. Is 50 mass% or more.

  The total amount of the hydroxy group-containing (meth) acrylic acid ester monomer and the dicarbonylimide derivative monomer is preferably 25% by mass or more and 90% by mass or less in 100% by mass of all monomers. More preferably, it is 50 mass% or more, More preferably, it is 55 mass% or more, More preferably, it is 60 mass% or more.

As the binder resin (B), 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meta ) Acrylate copolymer (copolymer (B0)) and the like.

The binder resin (B) may contain other binder resins as long as the effects of the present invention are exhibited.
The other binder resin may be a resin different from the copolymer (B0). For example, the copolymer having the structural unit (b1) and the structural unit (b2), the structural unit (b1) and the structural unit ( b2) a copolymer having a structural unit (b3), a copolymer having a structural unit (b1), a structural unit (b2) and a structural unit (b4), a structural unit (b1) and a structural unit (b2) A copolymer having a structural unit (b1), a structural unit (b4), a structural unit having an ethylenically unsaturated bond, a structural unit (b1), and another structural unit. And a copolymer having a structural unit having an ethylenically unsaturated bond.
The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group. A resin having such a structural unit can react with a group having the structural unit (b1) or the structural unit (b2) in a polymer having a structural unit derived from the structural unit (b1) or the structural unit (b2). It can be obtained by adding a monomer having an ethylenically unsaturated bond to the group.
As such a structural unit, a structural unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit, a structural unit obtained by adding 2-hydroxyethyl (meth) acrylate to a maleic anhydride unit, glycidyl (meta And a structural unit obtained by adding (meth) acrylic acid to an acrylate unit. Moreover, when these structural units have a hydroxy group, the structural unit which further added the carboxylic acid anhydride is also mentioned as a structural unit which has an ethylenically unsaturated bond.

As binder resin (B), 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meta ) Resin such as acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyltoluene copolymer, 3-methyl-3- ( Resin such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) Resin [K3] such as acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; benzyl (meta ) Resin with glycidyl (meth) acrylate added to acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin [K4] such as a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; tricyclodecyl (meth) acrylate / (Meth) acrylic acid reacts with glycidyl (meth) acrylate copolymer Resin [K5] such as a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate; tricyclodecyl (meth) acrylate / glycidyl Resin [K6] such as a resin obtained by further reacting a copolymer of (meth) acrylate with (meth) acrylic acid and further reacting with tetrahydrophthalic anhydride may be used.

The weight average molecular weight in terms of polystyrene of the resin (B) is usually from 3,000 to 100,000, preferably from 4,000 to 50,000, more preferably from 5,000 to 35,000, Preferably it is 5,000-30,000, Most preferably, it is 5,500-30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4, and still more preferably 1. 3 to 3.

The acid value (in terms of solid content) of the resin (B) is preferably 1 to 170 mg-KOH / g, more preferably 5 to 170 mg-KOH / g, and of these, 10 to 170 mg-KOH / g is preferable. Among these, 15 to 170 mg-KOH / g is preferable, 150 mg-KOH / g or less is more preferable, and 135 mg-KOH / g or less is more preferable.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  The content of the resin (B) is preferably 7 to 65% by mass, preferably 10 to 60% by mass, and more preferably 13 to 60% by mass, based on the total amount of solids. Of these, the content is preferably 17 to 60% by mass. When the content of the resin (B) is in the above range, a colored pattern can be easily formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

Polymerizable compound (C)
The polymerizable compound is a compound that can be polymerized by an active radical and / or acid generated from a polymerization initiator, and examples thereof include a polymerizable compound having an ethylenically unsaturated bond, and has a (meth) acrylic acid ester structure. Compounds are preferred. The polymerizable compound is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds.

Examples of polymerizable compounds having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, (A), (b) and (c). Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meta). ) Acrylate, bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- ( (Meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified di Intererythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate and caprolactone modified dipentaerythritol hexa (meth) An acrylate is mentioned.
Among these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

  The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

  Content of the polymeric compound (C) in the colored curable resin composition of this invention is 1-60 mass% normally with respect to the total amount of solid content, Preferably it is 5-50 mass%, More Preferably it is 10-40 mass%, More preferably, it is 12-35 mass%. The content ratio of the binder resin (B) and the polymerizable compound (C) (binder resin (B): polymerizable compound (C)) is usually 20:80 to 80:20 on a mass basis, preferably 35. : 65-80: 20. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

Polymerization initiator (D)
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat and starting polymerization, and a known polymerization initiator can be used.
The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and more preferably. Is a polymerization initiator containing an O-acyloxime compound.

  Examples of O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1- On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-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-di) Oxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl 6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine And at least one selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, and N-benzoyloxy-1- (4- More preferred is phenylsulfanylphenyl) octane-1-one-2-imine.

  Alkylphenone compounds include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one And 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.

  Alkylphenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, It may be -hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and benzyldimethyl ketal.

  As triazine compounds, 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-methyl) Phenyl) ethenyl -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acyl phosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl). ) -4,4 ′, 5,5′-tetraphenylbiimidazole (for example, see 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 (Trial Xylphenyl) 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-07-010913). Of these, compounds represented by the following formula and mixtures thereof are preferred.

  Other polymerization initiators include 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-4 ′. -Benzophenone compounds such as methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2- Examples include quinone compounds such as ethyl anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant described below (particularly an amine polymerization initiation assistant).

  Content of a polymerization initiator (D) is 0.1-40 mass parts normally with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C), Preferably it is 0.1-30. It is a mass part, More preferably, it is 1-30 mass parts, Most preferably, it is 1-20 mass parts.

<Polymerization initiation aid>
The polymerization initiation assistant is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D). When the colored curable resin composition of the present invention contains a polymerization initiation assistant, it is usually used in combination with a polymerization initiator (D).
Examples of the polymerization initiation assistant include amine polymerization initiation assistants, alkoxyanthracene polymerization initiation assistants, thioxanthone polymerization initiation assistants, and carboxylic acid polymerization initiation assistants.

  Examples of the amine polymerization initiation aid include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid Aminobenzoic acid esters such as 2-dimethylaminoethyl and 2-dimethylhexyl 4-dimethylaminobenzoate; N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4 ′ -Bis (diethylamino) benzophenone and 4,4'-bis (ethylmethylamino) benzophenone are mentioned, and alkylaminobenzophenone such as 4,4'-bis (diethylamino) benzophenone is preferred. Among these, alkylaminobenzophenone is preferable, and 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  As an alkoxyanthracene polymerization initiation assistant, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9, Examples include 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

  Examples of the thioxanthone polymerization initiation assistant include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  Carboxylic acid polymerization initiators include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenyl And sulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

  When using a polymerization initiation aid, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 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 initiation assistant is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>
A solvent (E) is not limited, The solvent normally used in the said field | area can be used individually or in combination of 2 or more types. Specifically, ester solvents (solvents containing —COO— in the molecule and not containing —O—), ether solvents (solvents containing —O— in the molecule and not containing —COO—), ether ester solvents (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O -, -CO- and -COO- free solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

  Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, pyruvin Examples include methyl acid, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  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, include phenetol and 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 and dipropylene glycol methyl ether acetate.

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

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

  Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

  Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

  Two or more of these solvents may be combined.

  Among the above solvents, an organic solvent having a boiling point of 120 ° C. or more and 210 ° C. or less at 1 atm is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol, N, N-dimethylformamide and N-methylpyrrolidone are preferred, propylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether, ethylene glycol monobutyl ether Dipropylene glycol methyl ether acetate, ethyl lactate, diacetone alcohol, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N, N- dimethylformamide and N- methylpyrrolidone is more preferred.

  Content of a solvent (E) is 45-95 mass% normally with respect to the total amount of a colored curable resin composition, Preferably it is 50-90 mass%, More preferably, it is 50-85 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. .

<Leveling agent>
Examples of the leveling agent include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

  Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (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 and TSF4460 (made by Momentive Performance Materials Japan GK) are listed.

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (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 in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) can be mentioned.

The content of the leveling agent is usually 0.0005% by mass or more and 0.6% by mass or less, preferably 0.001% by mass or more and 0.5% by mass or less, based on the total amount of the colored curable resin composition. More preferably 0.001% by mass to 0.2% by mass, still more preferably 0.002% by mass to 0.1% by mass, and particularly preferably 0.005% by mass to 0.07% by mass. It is below mass%. When the leveling agent content is within the above range, the flatness of the color filter can be improved.
The content of the leveling agent is usually from 0.001% by mass to 2.0% by mass, preferably from 0.002% by mass to 1.5% by mass, based on the total solid content of the colored curable resin composition. Or less, more preferably 0.004% by mass or more and 1.0% by mass or less, further preferably 0.008% by mass or more and 0.5% by mass or less, and particularly preferably 0.01% by mass or more and 0% by mass or less. .3% by mass or less.

<Other ingredients>
The colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a dye (Aa), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and, if necessary, leveling. It can be prepared by mixing an agent, a polymerization initiation assistant and other components. In addition to the dye (Aa), a colorant such as a pigment may be further mixed. The pigment is preferably mixed in advance with a part or all of the solvent (E) and used in the state of a pigment dispersion 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.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.

  The film thickness of the color filter to be produced can be appropriately adjusted according to the purpose and application, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm.

  As the substrate, a glass plate, a resin plate, silicon, or an aluminum, silver, silver / copper / palladium alloy thin film formed on the substrate is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

  The formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.

  First, a colored curable resin composition is applied on a substrate, dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained. Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.

  Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. Use an exposure device such as a mask aligner or stepper because it can irradiate parallel light uniformly over the entire exposure surface and perform precise alignment between the photomask and the substrate on which the colored composition layer is formed. Is preferred. A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide. The development method may be any of paddle method, dipping method and spray method. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

  It is preferable to further post-bake the resulting colored pattern. The color filter having a colored pattern or a colored coating film thus obtained may be further subjected to surface coating treatment in order to impart various characteristics.

  The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

Synthesis example 1
The following reaction was performed in a nitrogen atmosphere. After charging 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide into a flask equipped with a condenser and a stirrer, the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice-cooling, followed by stirring for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4′-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little and stirred at room temperature for 24 hours. The reaction solution was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours. When water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.8 parts of a compound represented by the formula (C-I-18).

  The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer is charged with 8.2 parts of the compound represented by the formula (BI-7), 10 parts of the compound represented by the formula (CI-18) and 20 parts of toluene. Then, 12.2 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170 parts of isopropanol. Next, the diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-18).

The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer, 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol were added, followed by stirring at room temperature for 30 minutes to prepare a blue solution. Next, after adding 396 parts of water to the blue solution, the mixture was further stirred at room temperature for 30 minutes to obtain a reaction solution.
A beaker is charged with 53 parts of water, and 11.8 parts of Keggin phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol are poured into the water and mixed at room temperature in an air atmosphere to prepare a phosphotungstic acid solution. Prepared.
The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. The mixture was further stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol and dispersed for 1 hour, followed by filtration twice. The operation of filtering the blue solid obtained by this operation in 200 parts of water and dispersing for 1 hour was repeated twice. The blue solid obtained by this operation was dried at 60 ° C. under reduced pressure to obtain 17.1 parts of a compound represented by the formula (AI-18).

Synthesis example 2
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was flowed with an appropriate amount of nitrogen to replace with a nitrogen atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C. with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (represented by the compound represented by the following formula (I-1) and the formula (II-1)) The compound was mixed at a molar ratio of 50:50.) A mixed solution of 25 parts, 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature, and a copolymer (resin (B type viscosity (23 ° C.)) 22 mPas, solid content 25.5%, solution acid value 28 mg-KOH / g B-1)) was obtained. The produced copolymer had a weight average molecular weight Mw of 7,700 and a molecular weight distribution of 2.1.

Synthesis example 3
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was flowed with an appropriate amount of nitrogen to replace with a nitrogen atmosphere, and 153 parts of ethyl lactate and 145 parts of propylene glycol monomethyl ether acetate were added and heated to 90 ° C. with stirring. Next, 17 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the above formula (I-1) and the formula (II-1)) The compounds were mixed at a molar ratio of 50:50.) A mixed solution of 23 parts, 144 parts of cyclohexylmaleimide, 46 parts of 2-hydroxyethyl methacrylate, and 381 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a mixed solution prepared by dissolving 3 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature, and a copolymer (resin (B type viscosity (23 ° C.) 15 mPas, solid content 24.6%, solution acid value 24 mg-KOH / g) B-2)) was obtained. The produced copolymer had a weight average molecular weight Mw of 5500 and a molecular weight distribution of 1.8.

Synthesis example 4
A 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer was flowed with an appropriate amount of nitrogen to replace the nitrogen atmosphere. 69 parts of ethyl lactate and 127 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C. with stirring. Next, 35 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the above formula (I-1) and the formula (II-1)) The compound was mixed at a molar ratio of 50:50.) A mixed solution of 69 parts, 115 parts of cyclohexylmaleimide, 12 parts of 2-hydroxyethyl methacrylate, and 482 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a mixed solution prepared by dissolving 3 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was kept at the same temperature for 3 hours, and then cooled to room temperature, and a copolymer (resin (B) viscosity (23 ° C.) 19 mPas, solid content 24.5%, solution acid value 26 mg-KOH / g B-3)) was obtained. The produced copolymer had a weight average molecular weight Mw of 7900 and a molecular weight distribution of 2.1.

Synthesis example 5
A 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer was flowed with an appropriate amount of nitrogen to replace with a nitrogen atmosphere. Next, 48 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the above formula (I-1) and the formula (II-1)) The compound was mixed at a molar ratio of 50:50.) A mixed solution of 24 parts, cyclohexylmaleimide 120 parts, 2-hydroxyethyl methacrylate 48 parts, and propylene glycol monomethyl ether acetate 318 parts was added dropwise over 5 hours. Meanwhile, a mixed solution prepared by dissolving 3 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 78 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 3 hours, and then cooled to room temperature. B-4)) was obtained. The produced copolymer had a weight average molecular weight Mw of 9400 and a molecular weight distribution of 2.4.

Synthesis Example 6
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was flowed with an appropriate amount of nitrogen to replace the nitrogen atmosphere. Next, 61 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the above formula (I-1) and the formula (II-1)) The compound was mixed at a molar ratio of 50:50.) A mixed solution of 23 parts, 123 parts of cyclohexylmaleimide, 23 parts of 2-hydroxyethyl methacrylate, and 343 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution prepared by dissolving 7 parts of 2,2-azobisisobutyronitrile in 198 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was kept at the same temperature for 3 hours, and then cooled to room temperature, and a copolymer (resin (B type viscosity (23 ° C.)) 27 mPas, solid content 25.0%, solution acid value 47 mg-KOH / g B-5)) was obtained. The produced copolymer had a weight average molecular weight Mw of 9400 and a molecular weight distribution of 2.4.

Synthesis example 7
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere. Subsequently, 55 parts of acrylic acid, 81 parts of N-cyclohexylmaleimide, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the following formula (I-1) and a formula (II The compound represented by -1) is mixed at a molar ratio of 50:50.) 224 parts, as well as tricyclo [5.2.1.0 ^2.6 ] decen-8-yl acrylate (formula (c-1) The compound represented by formula (c-2) and the compound represented by formula (c-2) are mixed at a molar ratio of 50:50.) 7 parts are dissolved in 140 parts of ethyl lactate to prepare a solution. It dropped in the flask kept at 70 degreeC using the dropping funnel over 4 hours. On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 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 solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw was 11.2 × 10 ³ , solid content 36.7%, A copolymer (resin (B-6)) solution having a value of 44 mg-KOH / g was obtained. It was 119 mg-KOH / g when solid content acid value was computed from said solid content and solution acid value.

Synthesis example 8
20 parts of the compound represented by the formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was heated at 110 ° C. Stir for 6 hours. The obtained reaction solution was cooled to room temperature, then added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour, whereby crystals were deposited. The precipitated crystals were obtained as a residue of suction filtration and then dried to obtain a compound represented by the formula (1-32).

Synthesis Example 9
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was flushed with an appropriate amount of nitrogen and replaced with a nitrogen atmosphere. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the above formula (I-1) and the formula (II-1)) Compound is mixed at a molar ratio of 50:50.) 25 parts, cyclohexylmaleimide 175 parts, 2-hydroxyethyl methacrylate 12 parts, ethyl lactate 295 parts, propylene glycol monomethyl ether acetate 180 parts over 3 hours It was dripped. On the other hand, a mixed solution prepared by dissolving 5 parts of a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature. (B-7)) A solution was obtained. The produced copolymer had a weight average molecular weight Mw of 7,600 and a molecular weight distribution of 2.2.

Synthesis Example 10
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was flowed with an appropriate amount of nitrogen to replace with a nitrogen atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C. with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the above formula (I-1) and the formula (II-1)) The compound was mixed at a molar ratio of 50:50.) A mixed solution of 25 parts, 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution prepared by dissolving 5 parts of a polymerization initiator 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature. (B-8)) A solution was obtained. The produced copolymer had a weight average molecular weight Mw of 8000 and a molecular weight distribution of 2.1.

About the measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the said binder resin, it carried out on condition of the following using GPC method.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Test solution concentration: 25 mg / mL (solvent: THF)
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 ratio of the weight average molecular weight and number average molecular weight obtained above in terms of polystyrene was defined as molecular weight distribution (Mw / Mn).

Examples 1-12 and Comparative Examples 1-2
Each component was mixed so that it might become a composition shown in Tables 5-7, and the colored curable resin composition was obtained.

¹⁾ A1-1 is a dispersant, mixed with B- ¹⁶⁾ and propylene glycol monomethyl ether acetate in the amount described in the column E- ¹⁸⁾ and used in a predispersed state.
²⁾ A1-2 is an acrylic pigment dispersant, B-67 ⁾ , and E- ¹⁸⁾ are mixed with propylene glycol monomethyl ether acetate in the amount described in the column, and used after being dispersed in advance.
³⁾ Total resin B-1 content is shown.
⁴⁾ Total resin B-6 content is shown.
⁵⁾ Indicates the total content of propylene glycol monomethyl ether acetate.

In Tables 5 to 7, each component represents the following. Moreover, binder resin (B) showed the mass part of solid content conversion.
Colorant (A); 1-1; Compound represented by Formula (1-32) Colorant (A); A1-1; Compound represented by AI-18 Colorant (A); A1-2 C. I. Pigment Blue 15: 6
Colorant (A); Pigment dispersion A; Pigment dispersion A obtained below
Dispersant: (BYK (registered trademark) -LPN6919 (by Big Chemie Japan)
Binder resin (B); B-1; Resin (B-1) (solid content conversion)
Binder resin (B); B-2; Resin (B-2) (solid content conversion)
Binder resin (B); B-3; Resin (B-3) (solid content conversion)
Binder resin (B); B-4; Resin (B-4) (solid content conversion)
Binder resin (B); B-5; Resin (B-5) (solid content conversion)
Binder resin (B); B-6; Resin (B-6) (solid content conversion)
Binder resin (B); B-7; Resin (B-7) (solid content conversion)
Binder resin (B); B-8; Resin (B-8) (solid content conversion)
Polymerizable compound (C); C-1; dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D); D-1; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; oxime compound)
Polymerization initiator (D); D-2; 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF; alkylphenone compound)
Polymerization initiator (D); D-3; 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure 369; manufactured by BASF; alkylphenone compound)
Polymerization initiation aid; D1-1; 2,4-diethylthioxanthone (KAYACURE DETX; manufactured by Nippon Kayaku Co., Ltd .; thioxanthone compound)
Solvent (E); E-1; Propylene glycol monomethyl ether acetate Solvent (E); E-2; Propylene glycol monomethyl ether Solvent (E); E-3; Dipropylene glycol methyl ether acetate Solvent (E); E-4 Diacetone alcohol solvent (E); E-5; ethyl lactate surfactant (F); F-1; polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Preparation of pigment dispersion A]
C. I. Pigment Blue 15: 6 10.0 parts Acrylic pigment dispersant 7.5 parts Propylene glycol monomethyl ether acetate 77.5 parts Ethyl lactate 5.0 parts are mixed, and the pigment is sufficiently dispersed using a bead mill. A pigment dispersion A was obtained.

<Preparation of colored pattern>
After applying each of the colored curable resin compositions of Examples 1 to 12 and Comparative Examples 1 and 2 on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, Pre-baked for minutes to form a colored composition layer. After allowing to cool, the distance between the substrate on which the colored composition layer is formed and the quartz glass photomask is set to 80 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 35 mJ / Light was irradiated with an exposure amount of cm ² (reference to 365 nm). A photomask having a 50 μm line and space pattern was used. The colored composition layer after light irradiation was immersed and developed in a developer (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction) at 25 ° C. for 60 seconds, After washing with water, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a colored pattern.

<Film thickness measurement>
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Tables 8 and 9.

<Chromaticity evaluation>
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE using the characteristic function of C light source (X, y) and brightness Y were measured. The results are shown in Tables 8 and 9.

<Colored pattern shape evaluation>
About the obtained coloring pattern, the shape was observed using the scanning electron microscope (S-4000; Hitachi High-Technologies Corporation make). In the case of the shape indicated by (p1) in FIG. 1 (so-called forward taper shape), it was indicated by ◯, when the shape indicated by (p2) was indicated by Δ, and when the shape indicated by (p3) was indicated by ×. When the inorganic film is laminated on the colored pattern, the shape shown by (p1) tends not to cause cracks or peeling. The results are shown in Tables 8 and 9.

[Preparation of pattern and observation of peeled piece]
A colored curable resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which this colored composition layer was formed and the quartz glass photomask having a pattern was set to 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), in an air atmosphere, Light irradiation was performed at an exposure amount of 150 mJ / cm ² (based on 365 nm). The colored composition layer after the light irradiation was developed by immersing in an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 23 ° C. for 80 seconds, and washed with water. The substrate after washing with water was observed using a microscope (magnification 500 times; VF-7510; manufactured by Keyence Corporation), and a peeling piece was formed on the portion corresponding to the unexposed portion of the colored composition layer formed on the substrate. The foreign material originating in was observed. The results are shown in Tables 8 and 9 as ◯ when no foreign matter was recognized and x when recognized.
Thereafter, post baking was performed in an oven at 230 ° C. for 30 minutes to obtain a colored pattern.

<Solubility evaluation>
A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and ethanol and then dried. A colored curable resin composition was spin-coated on this glass substrate, and then pre-baked at 100 ° C. for 3 minutes in a clean oven to form a colored composition layer.
Next, the substrate on which the colored composition layer has been formed is immersed in a developer at a liquid temperature of 25 ° C. (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction). The time when the 10 mm portion from the center of the substrate was completely dissolved was taken as the dissolution time, and the results are shown in Tables 8 and 9. The shorter the dissolution time, the better the solubility.

[Preparation of colored pattern]
Each of the colored curable resin compositions of Examples 10 to 12 and Comparative Example 2 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. Thus, a colored composition layer was formed. After cooling, the distance between the substrate on which the colored composition is formed and the photomask made of quartz glass is 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), 150 mJ / cm ^{2 in} an air atmosphere. Was irradiated with light at an exposure amount (365 nm reference). As a photomask, a mask on which a 100 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% nonionic surfactant and 2% sodium carbonate at 24 ° C. for 60 seconds, washed with water, and then in an oven at 230 ° C. for 30 minutes. Post-baking was performed to obtain a colored pattern.

  According to the colored curable resin composition of the present invention, a part of the colored composition layer after exposure is peeled off during development so that no foreign matter is formed, and a color filter having a good pattern shape can be provided.

Claims (8)

Containing a dye (Aa), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D);
A structural unit (b1) derived from at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, the binder resin (B);
A structural unit (b2) derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure;
A structural unit (b3) derived from a hydroxy group-containing (meth) acrylic acid ester monomer;
Copolymer der having a structural unit (b4) derived from the monomer of dicarbonyl imide derivative is,
The colored curable resin composition, wherein the monomer having an ethylenically unsaturated bond and a cyclic ether structure contains a compound represented by the following formulas (I) and (II) .
[In Formula (I) and Formula (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be. X ^b1 and X ^b2 represents a single ^{bond, * - R b3 -, *} - R b3 -O -, * - R b3 -S- or * -R ^b3 represents a -NH-.
R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]   The total amount of the hydroxy group-containing (meth) acrylic acid ester monomer and the dicarbonylimide derivative monomer is 25% by mass or more and 90% by mass or less in 100% by mass of all monomers. Colored curable resin composition. The hydroxy group-containing (meth) acrylic acid ester monomer is a hydroxyalkyl (meth) acrylic acid ester having an alkyl group having 1 to 10 carbon atoms,
The colored curable resin composition according to claim 1 or 2, wherein the monomer of the dicarbonylimide derivative is an N-substituted maleimide having a hydrocarbon group having 4 to 20 carbon atoms.   The colored curable resin composition according to any one of claims 1 to 3, further comprising a pigment (Ab). The dye (Aa) is a structural unit derived from an anion of a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen or an anion represented by the formula (A-II) The colored curable resin composition according to any one of claims 1 to 4, which is a compound comprising a polymer anion having a cation having a dye skeleton.
[In formula (A-II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom.
Y represents a divalent aliphatic hydrocarbon group, an arylene group, or a combination thereof, and the methylene group constituting the aliphatic hydrocarbon group may be replaced by an oxygen atom or a nitrogen atom.
R ⁶¹ represents a hydrogen atom or a methyl group. ] The colored curable resin composition according to any one of claims 1 to 5, wherein the dye (Aa) is a compound represented by the formula (AI).
[In the formula (AI), R ^{41 to} R ⁴⁴ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms which may have a substituent. A group in which an oxygen atom is inserted between methylene groups constituting the alkyl group, an aromatic hydrocarbon group which may have a substituent, an aralkyl group or hydrogen which may have a substituent Represents an atom. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom is inserted between methylene groups constituting the alkyl group. May be. R ⁴⁸ and R ⁵² may be bonded to each other to form —NH—, —O—, —S— or —SO ₂ —.
Ring T ¹ represents an aromatic heterocyclic ring which may have a substituent.
[Y] ^m− represents an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen, or an anion represented by the formula (A-II) The polymer anion which has the structural unit derived from is represented.
m represents an arbitrary natural number.
In addition, when two or more cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.
[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ have the same meanings as described above, respectively. ]
[In the formula (A-II), X, Y and R ⁶¹ have the same meanings as described above. ]]   The color filter formed from the colored curable resin composition in any one of Claims 1-6.   A liquid crystal display device comprising the color filter according to claim 7.