JP2019053303A - Red colored curable resin composition - Google Patents

Abstract

To provide a red colored curable resin composition that makes it possible to produce a red color filter with high lightness.SOLUTION: A red colored curable resin composition contains a colorant, a resin, a polymerizable compound and a polymerization initiator. The colorant is a colorant containing a compound represented by formula (1a), and at least one pigment selected from the group consisting of a yellow pigment, orange color pigment and red pigment.SELECTED DRAWING: None

Description

  The present invention relates to a red-colored curable resin composition.

The colored curable resin composition is used for the production of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. It is known to use a pigment or a dye as a coloring agent in this colored curable resin composition (Non-patent Document 1).

Suzuki Yakuji, "To the Understanding of Liquid Crystal Displays", First Edition, Nikkan Kogyo Shimbun, March 2005, p. 112

The red-colored curable resin composition is required to be able to produce a high-brightness red color filter.

The present invention includes the following inventions.
[1] containing a colorant, a resin, a polymerizable compound and a polymerization initiator,
The red colored curable resin composition which is a coloring agent in which a coloring agent contains the compound represented by Formula (1a), and at least 1 sort (s) of pigment chosen from the group which consists of a yellow pigment, an orange pigment, and a red pigment.
[In formula (1a), R ^{1 to} R ⁴ independently of each other represent a hydrogen atom, a C ^{1 to} C 20 monovalent saturated hydrocarbon group, or a C ^{6 to} C 10 carbon optionally having a substituent] Represents a monovalent aromatic hydrocarbon group, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the aromatic hydrocarbon The hydrogen atom contained in the group has 1 carbon atom
-CH _2- which may be substituted with an alkoxy group of -3 and is contained in the saturated hydrocarbon group
Is, -O -, - CO- or ^{-NR 11} - may be replaced by. R ¹ and R ² may combine with each other to form a ring containing a nitrogen atom together with the nitrogen atom to which they are attached, and R ³ and R ⁴ may combine with each other to form a nitrogen to which they are attached Together with the atoms, they may 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 +, -C
O ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ is represented.
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, plural R ^{5 s} 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 ⁺ .
R ⁸ represents a C 1 to C 20 monovalent saturated hydrocarbon group, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.
R ⁹ and R ¹⁰ each independently have a hydrogen atom or a carbon number of 1 to 2 which may have a substituent
0 represents a monovalent saturated hydrocarbon group, and -CH _2- contained in the saturated aliphatic hydrocarbon group is-
O -, - CO -, - NH- or -NR ⁸ - may have I placed conversion in, R ⁹ and R ^10, taken together, 3-10 membered together with the nitrogen atom to which they are attached It may form a nitrogen-containing heterocycle.
R ¹¹ independently represents a hydrogen atom, a monovalent C 1 to C 20 saturated hydrocarbon group, or a C 7 to C 10 aralkyl group. ]
[2] The pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 13
9, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. [1] The red colored curable resin composition according to [1], which is at least one selected from the group consisting of C.I.
[3] A red color filter formed of the red-colored curable resin composition according to [1] or [2].
[4] A display device including the red color filter according to [3].

According to the red colored curable resin composition of the present invention, a high brightness red color filter can be produced.

The red colored curable resin composition of the present invention comprises a colorant (A), a resin (B), and a polymerizable compound (C).
And a polymerization initiator (D).
The coloring agent (A) is a compound represented by the formula (1a) (hereinafter referred to as “compound (1a)”) and a pigment (A)
And 2). Furthermore, the colorant (A) is a dye (but different from the compound (1a)) (
Hereinafter, the dye may be referred to as "dye (A3)".
The red-colored curable resin composition of the present invention preferably further contains a solvent (E).
In addition, the red-colored curable resin composition of the present invention may optionally include at least one selected from the group consisting of a polymerization initiation auxiliary (D1) and a surfactant (F).
In the present specification, the compounds exemplified as each component can be used singly or in combination of two or more kinds unless otherwise noted.

<Colorant (A)>
The compound (1a) is represented by the formula (1a).
[In formula (1a), R ^{1 to} R ⁴ independently of each other represent a hydrogen atom, a C ^{1 to} C 20 monovalent saturated hydrocarbon group, or a C ^{6 to} C 10 carbon optionally having a substituent] Represents a monovalent aromatic hydrocarbon group, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the aromatic hydrocarbon The hydrogen atom contained in the group has 1 carbon atom
-CH _2- which may be substituted with an alkoxy group of -3 and is contained in the saturated hydrocarbon group
Is, -O -, - CO- or ^{-NR 11} - may be replaced by. R ¹ and R ² may combine with each other to form a ring containing a nitrogen atom together with the nitrogen atom to which they are attached, and R ³ and R ⁴ may combine with each other to form a nitrogen to which they are attached Together with the atoms, they may 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 +, -C
O ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ is represented.
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, plural R ^{5 s} 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 ⁺ .
R ⁸ represents a C 1 to C 20 monovalent saturated hydrocarbon group, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.
R ⁹ and R ¹⁰ each independently have a hydrogen atom or a carbon number of 1 to 2 which may have a substituent
0 represents a monovalent saturated hydrocarbon group, and -CH _2- contained in the saturated aliphatic hydrocarbon group is-
O -, - CO -, - NH- or -NR ⁸ - may have it placed conversion in, R ⁹ and R ¹⁰ are bonded to each other, together with the nitrogen atom to which they are attached 3-10 It may form a membered nitrogen-containing heterocycle.
R ¹¹ independently represents a hydrogen atom, a monovalent C 1 to C 20 saturated hydrocarbon group, or a C 7 to C 10 aralkyl group. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ^4, a phenyl group, toluyl group, xylyl group, mesityl group, a propyl phenyl and butyl phenyl group.
Examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom, -R ⁸ and -O.
_{^{H, -OR 8, -SO 3 -}} , -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 8, -SR 8,
_{^{-SO 2 R 8, -SO 3 R}} 8 and -SO ₂ NR ⁹ R ¹⁰ can be mentioned. Among them, as the _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ is preferably, -SO ₃ ^-
Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are more preferred. -SO ₃ in this case ^- Z ⁺ The, -SO ₃ ^{- +}
N (R ¹¹ ) ₄ is preferred. When R ^{1 to} R ⁴ are these groups, a red colored curable resin composition of the present invention containing the compound (1a) can form a color filter with less generation of foreign matter and excellent heat resistance.

A ring formed by R ¹ and R ² bonding together to form a nitrogen atom to which they are bonded, and R ³ and R ⁴ bonding together to form a nitrogen atom to which they are bonding Examples of the ring include the following.

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

Examples of -OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an icosyloxy group.

The -CO ₂ R ^8, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert- butoxycarbonyl group, and a hexyloxy group and icosyl oxycarbonyl group.

The -SR ^8, methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decyl alkylsulfanyl groups and equalize Sils Alpha group.
As -SO ₂ R ⁸ , a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an icosylsulfonyl group can be mentioned.
As —SO ₃ R ⁸ , a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group can be mentioned.

-SO ₂ NR ⁹ R ¹⁰ is a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2, 2-dimethylpropyl) sulfamoyl group, N
-(1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group,
N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N
-(3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N-
(1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexyl N-1-substituted sulfamoyl group such as sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-
Diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N
And N, N-disubstituted sulfamoyl groups such as N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, and N, N-heptylmethylsulfamoyl group.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms as R ⁹ and R ¹⁰ may have a substituent. The substituent includes a hydroxy group and a halogen atom.

R ⁹ and R ¹⁰ are bonded to each other to form a 3- to 10-membered nitrogen-containing heterocycle (in combination with a nitrogen atom)
A heterocycle) containing one or more nitrogen atoms in the ring may be formed. Examples of the heterocyclic ring include the following.

The _{^{R 5, -CO 2 H, -CO}} 2 - Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z
^+, -SO ₃ H and _-SO 2 NHR ⁹ are ^{_{preferred, -SO 3 -, -SO 3 -}} Z +, -SO
₃ H and -SO ₂ NHR ⁹ are more preferred.
As m, the integer of 1-4 is preferable and 1 and 2 are more preferable.

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

Examples of the aralkyl group having 7 to 10 carbon atoms as R ⁸ and R ¹¹ include a benzyl group, a phenylethyl group and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
At least two of four R ¹¹ as the above ⁺ N (R ¹¹ ) ₄ have one of 5 to 20 carbon atoms
It is preferable that it is a valent saturated hydrocarbon group. Moreover, the total carbon number of four R ¹¹ is 20 to 80.
Is preferably, and more preferably 20 to 60. ⁺ N in the compound (1a)
When (R ¹¹ ) ₄ is present, a color filter with few foreign substances can be formed from the red colored curable resin composition of the present invention containing the compound (1a) as R ¹¹ is these groups.

As the compound (1a), a compound represented by the formula (2a) (hereinafter sometimes referred to as "compound (2a)") is more preferable. Compound (2a) may be a tautomer thereof.

[In formula (2a), R ^{21 to} R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent] . R ²¹ and R ²² may be bonded to each other to form a ring containing a nitrogen atom together with the nitrogen atom to which they are bonded;
²³ and R ²⁴ may be bonded to each other to form a ring containing a nitrogen atom together with the nitrogen atom to which they are bonded.
R ²⁵ is, -SO ₃ ^- represents a Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.
m1 represents an integer of 0 to 5; When m1 is 2 or more, plural R ^{25 s} may be the same or different.
a1 represents an integer of 0 or 1;
X1 represents a halogen atom.
R ²⁶ represents a C 1-20 monovalent saturated hydrocarbon group.
Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁷ each independently represents a C 1-20 monovalent saturated hydrocarbon group or a benzyl group. ]

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{21 to} R ²⁴ includes the R ^{1 to} R ^4.
And the same groups as those mentioned as the aromatic hydrocarbon group. Hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, -SO 3 R 26 or -SO ₂ NH
R ²⁶ may be substituted.
As a combination of R ^{21 to} R ²⁴ , R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a C 6 to C 10 monovalent aromatic hydrocarbon group, and the aromatic hydrocarbon hydrogen atoms contained in the _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, those substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ preferred. A further preferable combination is a hydrogen contained in the aromatic hydrocarbon group, wherein R ²¹ and R ²³ are a hydrogen atom, R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. atom, -SO ₃ ^- in which are substituted with Z1 ⁺ or -SO ₂ NHR ^26.
When R ²¹ to R ²⁴ is with these groups, from the red colored curable resin composition of the present invention containing compound (2a), to form a color filter having excellent heat resistance.

A ring containing a nitrogen atom formed by R ²¹ and R ²² bonding to each other and forming a nitrogen atom to which they are bonded, and a nitrogen atom by which R ²³ and R ²⁴ bonding to each other and bonding to each other Examples of the ring containing a nitrogen atom which is formed together include the same rings as the ring which is formed together with the nitrogen atom to which R ¹ and R ² are bonded to each other. Among them, aliphatic heterocycles are preferred. Examples of the aliphatic heterocycle include the following.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ^27, include the same groups as those of the saturated hydrocarbon group R ⁸ to R ^11.
When R < ²¹ > -R < ²⁴ > is -R < ²⁶ >, it is preferable that -R < ²⁶ > is respectively independently a methyl group or an ethyl group. Further, as R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ^26, the
The C3-C20 branched alkyl group is preferable, a C6-C12 branched alkyl group is more preferable, and 2-ethylhexyl group is more preferable. When R ²⁶ is these groups,
From the red colored curable resin composition of the present invention containing the compound (2a), it is possible to form a color filter with less generation of foreign matter.

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
Among the four R ²⁷ , at least two of the four R ²⁷ may have 1 to 5 carbon atoms as the ⁺ N (R ²⁷ ) _4.
It is preferable that it is a valent saturated hydrocarbon group. Moreover, the total carbon number of four R ²⁷ is 20 to 80.
Is preferably, and more preferably 20 to 60. ⁺ N in the compound (2a)
When (R ²⁷ ) ₄ is present, a red-colored curable resin composition containing a compound (2a) in which R ²⁷ is a group of these can form a color filter with less occurrence of foreign matter.

  As m1, the integer of 1-4 is preferable and 1 and 2 are more preferable.

As the compound (1a), a compound represented by the formula (3a) (hereinafter sometimes referred to as “compound (3a)”) is more preferable. Compound (3a) may be a tautomer thereof.

[In formula (3a), R ³¹ and R ³² independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group has 6 to 6 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with 10 aromatic hydrocarbon groups or halogen atoms, and
It may be substituted by an alkoxy group having 1 to 3 carbon atoms, and is included in the saturated hydrocarbon group-
CH ₂ - is, -O -, - CO- or ^{-NR 11} - may be replaced by.
R ³³ and R ³⁴ 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 ³¹ and R ³³ may be combined with each other to form a ring containing a nitrogen atom together with R ^32, and R ³² and R ³⁴ may be combined with each other to form a ring together with a nitrogen atom And may form a ring containing
p and q each independently represent an integer of 0 to 5; When p is 2 or more, the plurality of R ³³ may be the same or different, and when q is 2 or more, the plurality of R ³⁴ may be the same or different.
R ¹¹ represents the same meaning as described above. ]

The monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ^32, include groups having 1 to 10 carbon atoms among those in R ^8.
As a C6-C10 aromatic hydrocarbon group which may be carried as a substituent, the same group as in R ¹ can be mentioned.
As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, and a propoxy group are mentioned.
R ³¹ and R ³² are preferably, independently of each other, a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

The alkyl group having 1 to 4 carbon atoms for R ³³ and R ^34, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a sec- butyl and tert- butyl groups.
The alkylsulfanyl group having 1 to 4 carbon atoms for R ³³ and R ^34, methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, a butyl alkylsulfanyl group and an isopropyl sulfanyl group.
The alkylsulfonyl group of 1 to 4 carbon atoms in R ³³ and R ^34, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group and a butylsulfonyl group and isopropylsulfonyl group.
Each of R ³³ and R ³⁴ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

  As p and q, the integer of 0-2 is preferable and 0 and 1 are more preferable.

Examples of the compound (1a) include compounds represented by Formula (1-1) to Formula (1-42). In the formula, R ⁴⁰ represents a C 1 to C 20 monovalent saturated hydrocarbon group, preferably a C 6 to C 12 branched alkyl group, and more preferably a 2-ethylhexyl group.

Compound (1a) is a commercially available xanthene dye (eg, “Ch” manufactured by Chuo Kasei Co., Ltd.).
ugai Aminol Fast Pink RH / C "," Rhodamin 6G "manufactured by Taoka Chemical Industry Co., Ltd. can be used. In addition, using a commercially available xanthene dye as a starting material, JP-A-2010-3
The compound can also be synthesized by reference to the publication 2999.

The pigment (A2) is a color index (published by The Society of Dyers and Colourists)
And at least one pigment selected from the group consisting of yellow pigments, orange pigments and red pigments.
For example, C.I. I. Pigment yellow 1, 3, 12, 13, 14, 15, 16, 17,
20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125,
128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 166
Yellow pigments such as 173, 194, 214;
C. I. Pigment oranges 13, 31, 36, 38, 40, 42, 43, 51, 55,
Orange pigments such as 59, 61, 64, 65, 71, 73;
C. I. Pigment red 9, 97, 105, 122, 123, 144, 149, 166
168, 176, 177, 180, 192, 209, 215, 216, 224, 242
, 254, 255, 264, 265, and the like. Other, C.I. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60, etc .; blue pigments such as C.I. I. Violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment green 7, 36, 58, etc .;
C. I. Brown pigments such as pigment brown 23, 25;
C. I. Black pigments such as pigment black 1 and 7 can also be included.

The pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C
. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. Pigment red 254, preferably at least one selected from the group consisting of C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. Pigment red 254 is more preferably at least one selected from the group consisting of C.I. The inclusion of the pigment facilitates optimization of the transmission spectrum as a red color filter, and the light resistance and chemical resistance of the color filter are improved.

The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group is introduced, grafting treatment to a pigment surface with a polymer compound or the like, and micronization by a sulfuric acid atomization method etc. A treatment, or a washing treatment with an organic solvent or water for removing impurities, a removal treatment of ionic impurities by an ion exchange method, or the like may be performed.
The pigment preferably has a uniform particle size. By containing the pigment dispersant and performing the dispersion process, it is possible to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solution.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants, and the like. These pigment dispersants may be used alone or in combination of two or more. As pigment dispersants, KP (Shin-Etsu Chemical Co., Ltd.), Floren (Kyoeisha Chemical Co., Ltd.), Solsparse (trade name) are trade names.
ZENECA (manufactured by KK), EFKA (manufactured by CIBA), AZSPAR (manufactured by Ajinomoto Elementary Techno), Disperbyk (manufactured by BYK Chemie), and the like.
When a pigment dispersant is used, the amount thereof used is preferably 1 with respect to the total amount of pigment (A2).
It is not less than mass% and not more than 100 mass%, more preferably not less than 5 mass% and not more than 50 mass%. When the amount of the pigment dispersant used is in the above range, a pigment dispersion in a uniformly dispersed state tends to be obtained.

The dye (A1) is not particularly limited, and known dyes can be used. Examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes and the like, and dyes which are soluble in organic solvents are preferable.
As the dye (A1), for example, color index (The Society of Dyers and Col
and the known dyes described in Dyeing Notes (Color Dyes Co., Ltd.). Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squalilium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline And dyes and nitro dyes. Among these, organic solvent soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62,
63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189;
C. I. Solvent red 45, 49, 111, 125, 130, 143, 145, 1
46, 150, 151, 155, 168, 169, 172, 175, 181, 207, 2
22, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38,
45, 47, 48, 51, 59, 60, etc. C.I. I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 23, 25, 29, 34, 3
6, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 1
12, 113, 114, 116, 119, 123, 128, 134, 135, 138, 1
39, 140, 144, 150, 155, 157, 160, 161, 163, 168, 1
69, 172, 177, 178, 179, 184, 190, 193, 196, 197, 1
99, 202, 203, 204, 205, 207, 212, 214, 220, 221, 2
28, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 31, 3
3, 34, 35, 37, 40, 42, 44, 57, 66, 73, 76, 80, 88, 97
, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145
, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195
, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252
, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280
281, 308, 312, 315, 316, 339, 341, 345, 346, 349
, 382, 383, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56,
62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid violet 6B, 7, 17, 19, 34, etc .; I. Acid dye,

C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50,
54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108
109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98,
99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 1
82, 184, 204, 207, 211, 213, 218, 220, 221, 222, 2
32, 233, 234, 241, 243, 246, 250;
C. I. Direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57
61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79,
80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, and so on. I.
Direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse violet 26, 27, etc. C.I. I. Disperse dye,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16; I. Reactive dye C.I. I. Mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 4
2, 43, 45, 56, 61, 62, 65;
C. I. Modred tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19
, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41,
43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 9
4, 95;
C. I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23,
24, 28, 29, 32, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31
, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58
Etc.
These dyes may be appropriately selected according to the spectrum of the desired color filter.

When a coloring agent (A) contains dye (A3), 1-90 mass% is preferable with respect to the total amount of coloring agent (A), and, as for content of dye (A3), 1-50 mass% is more preferable. .

The content ratio of the compound (1a) to the pigment (A2) is preferably 1:99 to 99: 1, more preferably 2:98 to 50:50, and still more preferably 5:95 to 30:70 on a mass basis.
With such a ratio, optimization of the transmission spectrum is facilitated, and the resulting color filter tends to be excellent in contrast, lightness, heat resistance and chemical resistance.

The content of the coloring agent (A) is preferably 5 to 60% by mass with respect to the total amount of solids,
More preferably, it is 8-50 mass%, More preferably, it is 10-40 mass%. When the content of the coloring agent (A) is within the above range, the color density of the color filter is sufficient, and the necessary amount of the resin (B) and the polymerizable compound (C) is contained in the composition. It is possible to form a color filter with sufficient mechanical strength.
Here, "the total amount of solid content" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the red-colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured, for example, by known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
Although resin (B) is not specifically limited, It is preferable that it is alkali-soluble resin. As resin (B), the following resin [K1]-[K6] etc. are mentioned, for example.
Resin [K1] unsaturated carboxylic acid and at least one selected from the group consisting of unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)"), cyclic ether structure having 2 to 4 carbon atoms And a copolymer of a monomer (b) (hereinafter sometimes referred to as "(b)") having an ethylenic unsaturated bond;
A monomer (c) copolymerizable with the resin [K2] (a) and (b), and (a) (however, (a)
And (b) are different. A copolymer with (hereinafter sometimes referred to as "(c)");
Copolymers of resins [K3] (a) and (c);
Resin obtained by reacting (b) with a copolymer of resin [K4] (a) and (c);
Resin obtained by reacting (a) with a copolymer of resin [K5] (b) and (c);
Resin obtained by reacting (a) with a copolymer of resin [K6] (b) and (c) and further reacting with a carboxylic anhydride.

Specifically as (a), 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 and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2
. 1] Hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [5 2
. 2.1] Bicyclo unsaturated compounds containing a carboxy group such as hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride,
4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3
, Unsaturated dicarboxylic acid anhydrides such as 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth)]
Unsaturated mono [(meth) acryloyloxyalkyl] esters of a polyvalent carboxylic acid having 2 or more valences such as acryloyloxyethyl];
Examples thereof include unsaturated acrylic acids having a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.
In the present specification, “(meth) acryloyl” represents at least one selected from the group consisting of acryloyl and methacryloyl. The notations such as "(meth) acrylic acid" and "(meth) acrylate" have the same meaning.

(B) is, for example, a polymerizable compound having a cyclic ether structure of 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond is there. (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
.

As (b), for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (
b1) (hereinafter sometimes referred to as “(b1)”), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b2)”), a tetrahydrofuryl group and ethylene The monomer (b3) (Hereinafter, it may be mentioned "(b3)") etc. which have an unsaturated bond, etc. are mentioned.

As (b1), a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized may be referred to as “(b1-1)” hereinafter. And a monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter referred to as “(b1-2)
Sometimes).

As (b1-1), glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p -Vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene , 2
2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2 , 3,5- tris (glycidyloxymethyl)
Styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) styrene.

As (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4
-Vinylcyclohexane (eg, Celoxide 2000; manufactured by Daicel Corporation), 3, 4
-Epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer A400
3,4-epoxycyclohexylmethyl (meth) acrylate (made by Daicel Co., Ltd.)
For example, Cyclomer M100 (manufactured by Daicel Co., Ltd.), a compound represented by Formula (I) and a compound represented by Formula (II) can be mentioned.

[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 It is also good.
X ^b1 and X ^b2 represents a single ^{bond, -R b3 -, * - R} b3 -O -, * - R b3 -S- or * -R ^b3 -
Represents NH-.
R ^b3 represents a C1-C6 alkanediyl group.
* Represents a bond with O. ]

As a C1-C4 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and a tert- butyl group are mentioned.
As an alkyl group in which a hydrogen atom is substituted by hydroxy, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy group -1-methylethyl group, 2-
Hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group,
3-hydroxybutyl group and 4-hydroxybutyl group are mentioned.
R ^b1 and R ^b2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

As the alkanediyl group, a methylene group, an ethylene group, a propane-1,2-diyl group,
Examples thereof include propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group.
Preferably, X ^b1 and X ^b2 are a single bond, a methylene group, an ethylene group, * -CH ₂ -O
-Or * -CH ₂ CH ₂ -O-, more preferably a single bond or * -CH ₂ CH ₂ -O
It is-(* represents a bond with O).

As a compound represented by Formula (I), the compound represented by either Formula (I-1)-Formula (I-15) is mentioned. Among them, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I)
-7), a compound represented by formula (I-9) or formula (I-11) to formula (I-15) is preferable, and a compound represented by formula (I-1), formula (I-7) or formula (I-) 9) or the compound represented by formula (I-15) is more preferable.

As a compound represented by Formula (II), the compound etc. which are represented by either Formula (II-1)-Formula (II-15) are mentioned. Among them, Formula (II-1), Formula (II-3), Formula (II)
-5), the compounds represented by the formula (II-7), the formula (II-9) or the formulas (II-11) to the formulas (II-15) are preferable, and the compounds represented by the formula (II-1), the formula (II-) 7), formula (II-9) or formula (I)
The compound represented by I-15) is more preferable.

The compound represented by Formula (I) and the compound represented by Formula (II) may be used alone or in combination in any ratio. When mixed and used, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5: 95 to 95 on a molar basis.
: 5, more preferably 10:90 to 90:10, still more preferably 20:80 to 80: 2
It is 0.

As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane And 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane and 3-ethyl-3-acryloyloxyethyl oxetane.

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

(B) is preferably (b1) in that the reliability such as heat resistance and chemical resistance of the color filter to be obtained can be further enhanced. Furthermore, (b1-2) is more preferable in that the storage stability of the red colored curable resin composition is excellent.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate,
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8
-Yl (meth) acrylate (in the art, the common name for “dicyclopentanyl (
It is said that "meta) acrylate". Moreover, it may be called "tricyclodecyl (meth) acrylate." ), Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth)
Acrylate (referred to in the art as “dicyclopentenyl (meth) acrylate” as a common name), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (Meta)
(Meth) acrylic esters such as acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-
2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] Hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2
. 2.1] Hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2
-Ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5
, 6-di (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6
-Dimethoxybicyclo [2.2.1] 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-t
ert-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- Bicyclo unsaturated compounds such as 2-ene;
N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N
Succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like Dicarbonyl imide derivatives;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene ,
Isoprene and 2,3-dimethyl-1,3-butadiene can be mentioned.
Among these, styrene, vinyl toluene, N-phenyl maleimide, N-cyclohexyl maleimide and N-benzyl maleimide are preferable in terms of copolymerization reactivity and heat resistance.

In the resin [K1], the ratio of structural units derived from each of them is the total structural unit constituting the resin [K1],
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40 to 98 mol%
Is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (b); 50 to 90 mol%
It is more preferable that
When the ratio of structural units of the resin [K1] is in the above range, the storage stability of the red-colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained colored pattern are obtained. It tends to be superior.

Resin [K1] can be prepared, for example, by the method described in the literature "Experimental method of polymer synthesis" (by Takayuki Otsu, Publisher, Chemical Co., Ltd., First Edition, First Edition, published on March 1, 1972) It can be manufactured with reference to the cited documents described in.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced by nitrogen to make an oxygen scavenging atmosphere, while stirring. The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, etc. used here are not specifically limited, What is usually used in the said field | area can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethyl valeronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) As a solvent, what is necessary is just to melt | dissolve each monomer, The solvent etc. which are mentioned later as a solvent (E) of the red colored curable resin composition of this invention are mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, may use a concentrated or diluted solution, or is taken out as a solid (powder) by a method such as reprecipitation. You may use one. In particular, by using the solvent contained in the red colored curable resin composition of the present invention as a solvent in the polymerization, the solution after reaction is used as it is for the preparation of the red colored curable resin composition of the present invention As a result, it is possible to simplify the production process of the red-colored curable resin composition of the present invention.

In the resin [K2], the ratio of structural units derived from each of them is the total structural unit constituting the resin [K2],
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
Is preferably
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of structural units of the resin [K2] is in the above range, the storage stability of the red-colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained colored pattern , Heat resistance and mechanical strength tend to be excellent.

The resin [K2] can be produced, for example, in the same manner as the method described for producing the resin [K1].

In the resin [K3], the ratio of structural units derived from each of them is the total structural unit constituting the resin [K3],
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c); 40 to 98 mol%
Is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (c); 50 to 90 mol%
It is more preferable that
The resin [K3] can be produced, for example, in the same manner as the method described for producing the resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and the carboxylic acid and / or carboxylic anhydride which (a) has a C2-C4 cyclic ether possessed by (b) It can be manufactured by adding it to
First, a copolymer of (a) and (c) is produced in the same manner as the method described for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as what was mentioned by resin [K3].

Next, a portion of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms which (b) has.
Subsequently to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b) a reaction catalyst of carboxylic acid or carboxylic acid anhydride with cyclic ether (for example, tris ( A resin [K4] may be produced by placing dimethylaminomethyl) phenol etc.) and a polymerization inhibitor (eg hydroquinone etc.) etc. in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours, for example. it can.
The amount of (b) to be used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). Within this range, the storage stability of the red-colored curable resin composition, the developability for forming a pattern, and the balance between solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are good. Tend to be Since the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain, as (b) used as the resin [K4], (b1
Is preferred, and (b1-1) is more preferred.
The amount of the reaction catalyst used is 0 based on 100 parts by mass of the total amount of (a), (b) and (c).
. 001 to 5 parts by mass is preferable. The amount of the polymerization inhibitor used is (a), (b) and (c)
0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of.
The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment and the calorific value due to the polymerization.

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

Furthermore, under the same conditions as in the method for producing the resin [K4], the carboxylic acid or carboxylic anhydride which (a) has in the cyclic ether derived from (b) which the copolymer of (b) and (c) has By reacting the product, a resin [K5] can be obtained.
The amount of (a) to be reacted with the above-mentioned copolymer is 5 to 80 with respect to 100 mol of (b)
Mol is preferred. Because the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain, as (b) used for the resin [K5], (b1) is preferable, and (b1-1) is more preferable.

The resin [K6] is a resin obtained by further reacting a carboxylic anhydride with the resin [K5].
The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether and the carboxylic acid or carboxylic acid anhydride.
As the carboxylic acid anhydride, maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, 1 And 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hemic anhydride), etc. Be The amount of use of the carboxylic acid anhydride is preferably 0.5 to 1 mole with respect to 1 mole of the amount of (a) used.

Specifically, as the resin (B), 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0
^2.6 ] Resins such as decyl 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-
Epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.
^02.6 ] decyl acrylate / (meth) acrylic acid / vinyl toluene / dicyclopentenyl (meth) acrylate copolymer, 3-methyl-3- (meth) acrylroyloxymethyl oxetane / (meth) acrylic acid / styrene Resins such as copolymers [K2];
Resin [K3] such as meta) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer; glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin containing glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / resin
Resin [K4] such as resin obtained by adding glycidyl (meth) acrylate to (meth) acrylic acid copolymer [K4]; copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid Resin [K5] such as resin obtained by reacting (meth) acrylic acid with a reacted resin, a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate, etc .; tricyclodecyl (meth) acrylate / Resin [K6] etc., such as resin which made tetrahydrophthalic anhydride react further with the resin which made (meth) acrylic acid react the copolymer of glycidyl (meth) acrylate, etc. are mentioned.

Among them, as the resin (B), resin [K1], resin [K2] and resin [K3] are preferable.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,
000, more preferably 5,000 to 50,000, still more preferably 5,
0000-30,000. 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 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, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg KOH / g, more preferably 60 to 150 KOH / g, and still more preferably 70 to 135 mg KOH / g.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined, for example, by titration using a potassium hydroxide aqueous solution.

The content of the resin (B) is preferably 7 to 7% of the solid content of the red-colored curable resin composition.
It is 65 mass%, more preferably 13 to 60 mass%, still more preferably 17 to 5
It is 5% by mass. When the content of the resin (B) is in the above range, the solubility of the unexposed area in the developer tends to be high.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acid or the like generated from the polymerization initiator (D) by the action of light or heat, and for example, a polymerizable ethylenic unsaturated bond The compound etc. which it has are mentioned, Preferably a (meth) acrylic acid ester compound is mentioned.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. As such a polymerizable compound, trimethylolpropane 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 dipentaerythritol 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) acrylate. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (
Meta) acrylate is preferred.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, with respect to the total amount of solids.
It is. When the content of the polymerizable compound (C) is in the above range, the residual film ratio of the colored pattern and the chemical resistance 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 active radicals, acids and the like by the action of light and heat and initiating polymerization, and known polymerization initiators can be used.
Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acyl phosphine oxide compounds, O-acyl oxime compounds and biimidazole compounds.

The O-acyl oxime compound is a compound having a partial structure represented by formula (d1).
Hereinafter, * represents a bond.
As the O-acyl oxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-
Phenylsulfanylphenyl) octan-1-one-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-dioxacyclopentanyl) Methyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-
Acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-
3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1-
[9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-
Mention may be made of cyclopentylpropan-1-one-2-imine. You may use commercial products, such as Irgacure (registered trademark) OXE01, OXE02 (above, BASF Corporation make), N-1919 (ADEKA company make), etc.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). The benzene ring in these partial structures may have a substituent.

As a compound having a partial structure represented by the formula (d2), 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] butane -1- on is mentioned. Irgacure (registered trademark) 369, 907 and 3
You may use commercial items, such as 79 (above, BASF Corporation make).
As a compound having a partial structure represented by the formula (d3), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxy) Ethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and And benzyl dimethyl ketal.
From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by Formula (d2).

Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 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, 2,2,3
4-Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,
5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl)- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine is mentioned.

As an acyl phosphine oxide compound, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide is mentioned. Irgacure (registered trademark) 819 (BASF
Commercial products, such as company made), may be used.

As a biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ',
5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (e.g., JP-A-6-7537)
See JP 2 and JP 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 (trialkoxyphenyl) biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.) and the phenyl group at the 4,4'5,5'-position are carboalkoxy groups. Substituted imidazole compounds (e.g.
No. 10913).

Furthermore, as a polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- 4'-methyl diphenyl sulfide, 3,3 ', 4,
4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-
Benzophenone compounds such as trimethylbenzophenone; 9,10-phenanthrenequinone, quinone compounds such as 2-ethylanthraquinone, camphorquinone; 10-butyl-2-
Examples include chloroacridone, benzyl, methyl phenylglyoxylate and titanocene compounds. It is preferable to use these in combination with the below-mentioned polymerization start auxiliary (D1) (especially amines).

As an acid generator, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate,
4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate And onium salts such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylates and benzoin tosylates.

As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acyl phosphine oxide compounds, O-acyl oxime compounds and biimidazole compounds is preferable, and O-acyloxy is preferable. The polymerization initiator containing a sulfur compound is more preferable, and the polymerization initiator containing an O-acyloxime compound and an alkylphenone compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part. When the content of the polymerization initiator (D) is in the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity is improved.

<Polymerization start assistant (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to accelerate the polymerization of the photopolymerizable compound whose polymerization has been initiated by the polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation auxiliary (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate,
2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl paratoluidine, 4
, 4'- bis (dimethylamino) benzophenone (commonly called Michler's ketone), 4,4'-
Bis (diethylamino) benzophenone and 4,4'-bis (ethylmethylamino) benzophenone are mentioned, and among them, 4,4'-bis (diethylamino) benzophenone is preferred. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

As an alkoxyanthracene compound, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxy Anthracene and 2-
Ethyl-9,10-dibutoxyanthracene is mentioned.

As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4- dichloro thioxanthone, and 1-chloro- 4-propoxy thioxanthone are mentioned.

Examples of carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

As a polymerization start adjuvant (D1), a thioxanthone compound is preferable.
Moreover, when using a polymerization start auxiliary (D1), the usage-amount is preferably 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), and more Preferably, it is 1 to 20 parts by mass. Moreover, Preferably it is 20-100 mass parts with respect to 100 mass parts of content of a polymerization initiator (D), More preferably, it is 30-80 mass parts. Polymerization start assistant (D
When the amount of 1) is in this range, a pattern can be formed with high sensitivity, and a color filter with higher brightness tends to be obtained.

<Solvent (E)>
The solvent (E) is not particularly limited, and solvents commonly used in the relevant field can be used. For example, ester solvents (solvents containing -COO- in the molecule but not -O-), ether solvents (solvents containing -O- in the molecule and not -COO-), ether ester solvents (solvents not containing -COO-)
Solvents containing -COO- and -O- in the molecule), ketone solvents (including -CO- in the molecule,-
Solvents that do not contain COO-), alcohol solvents (solvents that contain OH in the molecule but do not contain -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide can be mentioned.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, butyl butyrate, isopropyl butyrate, butyric acid Examples include butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

As the ether solvent, 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, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dipropyl ether, anisole, phenetole and methyl anisole Can be mentioned.

As the ether ester solvent, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, 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 and diethylene glycol monobutyl ether acetate .

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone,
2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone.

As said alcohol solvent, methanol, ethanol, propanol, butanol,
Hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin are included.

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

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

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm (101.325 kPa) is preferable in terms of coating property and drying property. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-
Methyl-2-pentanone and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and Ethyl 3-ethoxypropionate is more preferred.

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

<Surfactant (F)>
As surfactant (F), silicone type surfactant, fluorochemical surfactant, and silicone type surfactant which has a fluorine atom are mentioned. These may have a polymerizable group in the side chain.

As said silicone type surfactant, surfactant which has a siloxane bond is mentioned. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH
21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH8400 (Toray,
Dow Corning Co., Ltd. product, KP 321, KP 322, KP 323, KP 324, KP 3
26, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401
, TSF 410, TSF 4300, TSF 4440, TSF 4445, TSF-4446
, TSF 4452 and TSF 4460 (manufactured by Momentive Performance Materials Japan GK).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M (
Co., Ltd.), Megafuck (registered trademark) F 142 D, F 171, F 172, F 173
, F177, F183, F554, R30, RS-718-K (DIC Corporation)
Products), F-top (registered trademark) EF301, the same EF303, the same EF351, the same EF352
(Mitsubishi Materials Electronics Kasei Co., Ltd.), Surflon (registered trademark) S381, S382,
Examples thereof include SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), and the like.

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

The content of the surfactant (F) is preferably 0.00 to the red-colored curable resin composition.
1% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass
The content is more preferably 0.01% by mass or more and 0.05% by mass or less. However, the content of the pigment dispersant is not included in the content of the surfactant (F). When the content of the surfactant (F) is in the above range, the flatness of the coating can be improved.

<Other ingredients>
The red-colored curable resin composition of the present invention may optionally contain fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc. May contain additives known in the art.

<Method of producing red-colored curable resin composition>
The red colored curable resin composition of the present invention is used, for example, as a compound (1a), a pigment (A2), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and as required It can be prepared by mixing the dye (A3), the polymerization initiator (D1), the solvent (E), the surfactant (F) and other components.
The pigment (A2) is previously mixed with part or all of the solvent (E), and the average particle size of the pigment is 0.2
Dispersion is preferably performed using a bead mill or the like until the particle size is about μm or less. At this time, part or all of the pigment dispersant and the resin (B) may be blended, if necessary. In the obtained pigment dispersion, the compound (1a), the remainder of the resin (B), the polymerizable compound (C) and the polymerization initiator (D)
), The remainder of the solvent (E), and optionally the dye (A3), the polymerization initiator (D)
The target red colored curable resin composition can be prepared by mixing the polymerization start auxiliary (D1), the surfactant (F), and the other components so as to have predetermined concentrations.
When the dye (A3) is contained, the dye (A3) and the compound (1a) may be previously dissolved in part or all of the solvent (E) to prepare a solution. The solution has a pore size of 0.01 to 1 μm
It is preferred to filter with a degree of filter.
The red colored curable resin composition prepared by mixing as described above was used to have a pore size of 0.1 to 10 μm.
It is preferred to filter with a degree of filter.

<Method of manufacturing red color filter>
As a method of manufacturing the coloring pattern of a red color filter from the red coloring curable resin composition of this invention, a photolithographic method, the inkjet method, the printing method, etc. are mentioned. Among them, photolithographic method is preferred. The photolithographic method is a method in which the red colored curable resin composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed and developed through a photomask. In the photolithographic method, a colored coating film which is a cured product of the above composition layer can be formed by not using a photomask during exposure and / or not developing.
The film thickness of the red color filter to be produced is not particularly limited, and can be appropriately adjusted depending on the purpose, application and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0. 5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica on the surface, a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate, silicon, the substrate An aluminum, silver, silver / copper / palladium alloy thin film or the like is used. Other color filter layers, resin layers, transistors, circuits and the like may be formed on these substrates.

The formation of each color pixel by photolithography can be carried out using known or conventional equipment and conditions. For example, it can produce as follows.
First, a red-colored curable resin composition is applied onto a substrate, dried by heating (pre-baking) and / or reduced pressure to remove volatile components such as a solvent and drying to obtain a smooth composition layer.
As a coating method, a spin coat method, a slit coat method, a slit and spin coat method, etc. may be mentioned.
30-120 degreeC is preferable and, as for the temperature in the case of performing heat-drying, 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable that it is 10 seconds-60 minutes, and 30 seconds-3
More preferably, it is 0 minutes.
When drying under reduced pressure, it is preferable to carry out at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa.
The film thickness of the composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target red color filter.

Next, the composition layer is exposed through a photomask to form a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended application is used.
As a light source used for exposure, the light source which generate | occur | produces the light of a 250-450 nm wavelength is preferable. For example, light less than 350 nm is cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm is selectively extracted using a band pass filter that extracts these wavelength ranges. You may Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp and the like can be mentioned.
It is preferable to use an exposure apparatus such as a mask aligner and a stepper because the entire exposure surface can be uniformly irradiated with parallel rays and accurate alignment between the photomask and the substrate can be performed.

A colored pattern is formed on the substrate by bringing the composition layer after exposure into contact with a developer and developing. By development, the unexposed part of the composition layer is dissolved in the developer and removed. As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethyl ammonium hydroxide, is preferable, for example. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.0.
It is 3 to 5% by mass. Furthermore, the developer may contain a surfactant.
The developing method may be any of a paddle method, a dipping method, a spray method and the like. Furthermore, the substrate may be inclined at any angle during development.
After development, washing with water is preferred.

Further, post-baking is preferably performed on the obtained colored pattern. 150-250 degreeC is preferable and, as for post-baking temperature, 160-235 degreeC is more preferable. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

The colored pattern and the colored coating film thus obtained are useful as a red color filter. According to the red-colored curable resin composition of the present invention, a red color filter having particularly high brightness can be produced, so that the red color filter is a display device (for example, a liquid crystal display device, an organic EL device, etc.) It is useful as a red color filter used for electronic paper, a solid-state imaging device, etc.

The present invention will now be described more specifically by the following examples. In the examples,% and parts representing contents or amounts used are by mass unless otherwise specified.
In the following, the structure of the compound is mass spectrometry (LC; Agilent model 1200, MAS
S: confirmed by Agilent LC / MSD type).

Synthesis Example 1
A mixture of 12 parts of a compound represented by the formula (1x), 60 parts of N-methyl-2-pyrrolidone and 12.6 parts of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed at 60 ° C. Stir for hours. The above reaction solution was cooled to room temperature, added to a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals are obtained as the residue of suction filtration and then dried to obtain the formula (1
12.4 parts of compounds represented by -47) were obtained. The yield was 83%.

Identification of compound represented by formula (1-47) (mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 503.4
Exact Mass: 502.2

Synthesis Example 2
15 parts of a compound represented by the formula (1x), 75 parts of N-methyl-2-pyrrolidone and 25.8 parts of decahydroquinoline (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, and the obtained mixture is heated to 110 ° C. The mixture was stirred for 24 hours. The above reaction solution was cooled to room temperature, added to a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue of suction filtration and then dried to obtain 19.5 parts of a compound represented by the formula (1-49). The yield was 86%.

Identification of compound represented by formula (1-49) (mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 611.4
Exact Mass: 610.3

Synthesis Example 3
20 parts of a compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed under light shielding condition, and the obtained solution is stirred at 110 ° C. for 6 hours did. The resulting reaction solution was cooled to room temperature, 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, crystals were precipitated. The precipitated crystals were obtained as the residue of suction filtration and then dried to obtain 24 parts of a compound represented by the formula (1-50). The yield was 80%.

Identification of compound represented by formula (1-50) (mass spectrometric analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

Synthesis Example 4
12 parts of a compound represented by the formula (1x), 60 parts of N-methyl-2-pyrrolidone and 14.7 parts of 1-methylpiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, and the obtained mixture is Stir at 5 ° C for 5 hours. The above reaction solution was cooled to room temperature, added to a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were collected as a residue of suction filtration and then dried to obtain 13.8 parts of a compound represented by the formula (1-48). The yield was 88%.

Identification of compound represented by formula (1-48) (mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 531.2
Exact Mass: 530.2

Synthesis Example 5
The compound represented by the formula (A1-1a) and the formula (A1-1a) were added to a flask equipped with a condenser and a stirrer.
A1-1b) 15 parts of a mixture (trade name: Chugai Aminol Fast Pink R; manufactured by Chuo Kasei Co., Ltd.), 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide are added, and the mixture is stirred at 20 ° C. or less Was added dropwise with 10.9 parts of thionyl chloride. After completion of the dropwise addition, the temperature was raised to 50 ° C., and the reaction was maintained at this temperature for 5 hours for reaction, and then cooled to 20 ° C. While the reaction solution after cooling is maintained at 20 ° C. or less with stirring, 2-ethylhexylamine 12.
A mixture of 5 parts and 22.1 parts of triethylamine was added dropwise. Then, it was made to react, stirring at the same temperature for 5 hours. Next, the reaction mixture obtained was evaporated using a rotary evaporator, and then a small amount of methanol was added and vigorously stirred. This mixture is deionized water 375
The mixture was added with stirring into a mixed solution to precipitate crystals. The precipitated crystals are separated by filtration, washed well with ion-exchanged water, and dried at 60 ° C. under reduced pressure to obtain a dye (a) (formula (A1-1-1)
11.3 parts of a mixture of compounds represented by 1-1-8) were obtained.

Synthesis Example 6
0.02 L of nitrogen in a flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel
Per minute with nitrogen atmosphere, propylene glycol monomethyl ether acetate 30
5 parts were charged and heated to 70 ° C. with stirring. Next, 60 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) Compounds are mixed in a molar ratio of 50:50.) 44
A solution was prepared by dissolving 0 part in 140 parts of propylene glycol monomethyl ether acetate, and the solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.
On the other hand, a solution of 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate was added to the flask over 4 hours using another dropping funnel. It dripped. After the addition of the solution of the polymerization initiator is completed, the temperature is maintained at 70 ° C. for 4 hours, and then cooled to room temperature, and the weight average molecular weight (Mw) is
1 × 10 ³ , molecular weight distribution is 2.16, solid content is 34.8%, acid value in terms of solid content is 81 mg K
A resin B1 solution of OH / g was obtained. Resin B1 has a structural unit shown below.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example is as follows:
It carried out on condition of the following using GPC method.
Device: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40,
F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
Ratio (Mw / Mn) of weight average molecular weight and number average molecular weight of polystyrene conversion obtained above
) Was the molecular weight distribution.

Examples 1 to 12
Each component was mixed so that it might become the composition shown in Table 1 and Table 2, and the red colored curable resin composition was obtained.

¹⁾ pigment is mixed with propylene glycol monomethyl ether acetate in an amount of pigment dispersing agent, and E-1 ²⁾ column described were pre-dispersed.
²⁾ E-12 ²⁾ represents the sum of propylene glycol monomethyl ether acetate content.

¹⁾ pigment is mixed with propylene glycol monomethyl ether acetate in an amount of pigment dispersing agent, and E-1 ²⁾ column described were pre-dispersed.
²⁾ E-12 ²⁾ represents the sum of propylene glycol monomethyl ether acetate content.

In Tables 1 and 2, each component represents the following. Moreover, resin (B) showed the mass part of solid content conversion.
Compound (1a): A1-1: Compound Represented by Formula (1-47) Compound (1a): A1-2: Compound Represented by Formula (1-49) Compound (1a): A1-3: Formula Compound Represented by (1-50) Compound (1a): A1-4: Compound Represented by Formula (1-48) Compound (1a): A1-5: Compound Represented by Formula (1-41) Compound (1a): A1-6: Compound represented by Formula (1-37) Pigment (A2): A2-1: C.I. I. Pigment red 254
Pigment (A2): A2-2: C.I. I. Pigment red 242
Pigment (A2): A2-3: C.I. I. Pigment red 177
Resin (B): Resin B1
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (
Registered trademark DPHA; Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-1919 (manufactured by Adeka; O-acyloxime compound)
Polymerization start auxiliary (D1): 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D2): OXE01 (Ciba Specialty Chemicals)
Solvent (E): E-1: Propylene glycol monomethyl ether acetate Solvent (E): E-2: Propylene glycol monomethyl ether Solvent (E): E-3: Diacetone alcohol Surfactant (F): Fluorine-based surfactant Agent (Megafuck (registered trademark) F 554; DIC
(Made by)

[Preparation of colored pattern]
The red colored curable resin composition was applied by spin coating on a 2 inch square glass substrate (Eagle XG; manufactured by Corning), and then prebaked at 100 ° C. for 3 minutes to form a composition layer. After leaving to cool, the distance between the composition layer on the substrate and the quartz glass photomask having a pattern is set to 100 μm using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.).
The light was irradiated at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. In addition, the mask in which the 100 micrometer line and space pattern was formed was used as a photomask. After light irradiation, the above-mentioned coating film is developed by immersion in an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 23 ° C. for 80 seconds, and after water washing, in an oven at 230 ° C. for 20 minutes. Post-baking was performed to obtain a colored pattern.

[Film thickness measurement]
About the obtained colored pattern, a film thickness measuring device (DEKTAK3; Japan Vacuum Technology Co., Ltd.)
Film thickness was measured. The results are shown in Table 3.

[Chromaticity evaluation]
About the coloring pattern on the obtained glass substrate, a spectrum is measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS Co., Ltd.), and the CIE XYZ color system using a C light source color matching function Xy chromaticity coordinates (x, y) and tristimulus values Y at. The larger the value of Y, the higher the lightness. The results are shown in Table 3.

[Contrast evaluation]
An operation was performed in the same manner as the formation of the colored pattern except that exposure was performed without using a photomask and development was not performed, to prepare a colored coating film on a glass substrate. About the colored coating film on the obtained glass substrate, a contrast colorimeter (CT-1; manufactured by Toshisaka Electric Co., Ltd., detector; BM-5A, light source; F
The contrast was measured with a blank value of 30,000 using -10). The colored film on the glass substrate was sandwiched between polarizing films (POLAX-38S; manufactured by RUKEO Co., Ltd.) to obtain a measurement sample. The results are shown in Table 3.

Example 13
A red-colored curable resin composition is prepared in the same manner as in Example 1 except that the compound represented by the formula (1-47) is replaced with the dye (a). The red colored curable resin composition is subjected to the same operation as in Example 1 to obtain a high-brightness colored pattern.

Example 14
The compound represented by the formula (1-47) is C.I. I. A red colored curable resin composition is prepared in the same manner as in Example 1 except that the acid red 52 is substituted. The red colored curable resin composition is subjected to the same operation as in Example 1 to obtain a high-brightness colored pattern.

According to the red colored curable resin composition of the present invention, a high brightness red color filter can be produced.

Claims (4)

Containing a coloring agent, a resin, a polymerizable compound and a polymerization initiator,
The red colored curable resin composition which is a coloring agent in which a coloring agent contains the compound represented by Formula (1a), and at least 1 sort (s) of pigment chosen from the group which consists of a yellow pigment, an orange pigment, and a red pigment.
[In formula (1a), R ^{1 to} R ⁴ independently of each other represent a hydrogen atom, a C ^{1 to} C 20 monovalent saturated hydrocarbon group, or a C ^{6 to} C 10 carbon optionally having a substituent] Represents a monovalent aromatic hydrocarbon group, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the aromatic hydrocarbon The hydrogen atom contained in the group has 1 carbon atom
-CH _2- which may be substituted with an alkoxy group of -3 and is contained in the saturated hydrocarbon group
Is, -O -, - CO- or ^{-NR 11} - may be replaced by. R ¹ and R ² may combine with each other to form a ring containing a nitrogen atom together with the nitrogen atom to which they are attached, and R ³ and R ⁴ may combine with each other to form a nitrogen to which they are attached Together with the atoms, they may 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 +, -C
O ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ is represented.
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, plural R ^{5 s} 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 ⁺ .
R ⁸ represents a C 1 to C 20 monovalent saturated hydrocarbon group, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.
R ⁹ and R ¹⁰ each independently have a hydrogen atom or a carbon number of 1 to 2 which may have a substituent
0 represents a monovalent saturated hydrocarbon group, and -CH _2- contained in the saturated aliphatic hydrocarbon group is-
O -, - CO -, - NH- or -NR ⁸ - may have it placed conversion in, R ⁹ and R ¹⁰ are bonded to each other, together with the nitrogen atom to which they are attached 3-10 It may form a membered nitrogen-containing heterocycle.
R ¹¹ independently represents a hydrogen atom, a monovalent C 1 to C 20 saturated hydrocarbon group, or a C 7 to C 10 aralkyl group. ] The pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C
. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. The red colored curable resin composition according to claim 1, which is at least one selected from the group consisting of C.I. A red color filter formed of the red colored curable resin composition according to claim 1.   A display device comprising the red color filter according to claim 3.