KR20130041735A - A colored curable resin composition - Google Patents

Abstract

PURPOSE: A coloring curable resin composition is provided to manufacture a green color filter showing green color with high brightness by using a coloring agent containing chlorinated copper phthalocyanine pigment and a yellow pigment. CONSTITUTION: A coloring curable resin composition comprises a coloring agent, resin, a polymerizable compound and a polymerization initiator. The coloring agent includes chlorinated copper phthalocyanine pigment and a yellow pigment. The content of the yellow pigment is 1-65 mass% or less to the total amount of the coloring agent. The chlorinated copper phthalocyanine pigment includes the compound represented by chemical formula P1. In the chemical formual P1, a1, a2, a3 and a4 respectively represent an integer of 0-4, and (a1+a2+a3+a4) is 10-16. The chlorinated copper phthalocyanine pigment is C.I. pigment green 7. The yellow pigment is yellow azo pigment. The yellow azo pigment includes the compound represented by chemical formula ).

Description

Colored curable resin composition {A COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

Colored curable resin composition is used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display panel, an electroluminescent panel, and a plasma display panel. As such colored curable resin composition, C.I Pigment Green 7 and C.I. Colored curable resin compositions containing only Pigment Yellow 138 are known (for example, JP2009-265641-A).

When the above-mentioned colored curable resin composition manufactures a blueish green color filter with the said composition, the brightness of this color filter may not necessarily be fully satisfied.

The present invention includes the following inventions.

[1] a colored curable resin composition comprising a coloring agent, a resin, a polymerizable compound and a polymerization initiator,

The colorant comprises a copper chloride phthalocyanine pigment and a yellow dye,

Content of a yellow dye is 1 mass% or more and 65 mass% or less with respect to the total amount of a coloring agent.

[2] The colored curable resin composition according to [1], wherein the chlorinated phthalocyanine pigment is a pigment containing a compound represented by formula (P1).

[In formula (P1), a1, a2, a3 and a4 represent the integer of 0-4 independently of each other, and (a1 + a2 + a3 + a4) is 10 or more and 16 or less.]

[3] The copper chloride phthalocyanine pigment is C.I. Colored curable resin composition as described in [1] which is Pigment Green 7.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the yellow dye is a yellow azo dye.

[5] The colored curable resin composition according to [4], wherein the yellow azo dye is a dye containing a compound represented by formula (1).

[In Formula (1), A <^0> represents the C6-C14 bivalent aromatic hydrocarbon group which may have a substituent.

B <^0> represents the C6-C14 monovalent heterocyclic group which may have a substituent, and may have a C6-C14 monovalent aromatic hydrocarbon group or substituent.

R <^51> represents the C1-C18 acyl group which may have a hydrogen atom and a substituent, and may have a C1-C16 monovalent saturated hydrocarbon group or a substituent.

p1 represents 1 or 2. When p1 is 2, some A <^0> , B <^0> , R <^51> and R <^52> may mutually be same or different.

If p1 is 1, R ⁵² is, although a hydrogen atom or a substituent group represents a good monovalent saturated hydrocarbon group having 1 to 16 carbons, when p1 is 2, R ⁵² is even have a substituent divalent group having a carbon number of 1 to 35 The saturated hydrocarbon group may be represented and -CH ₂ -contained in the monovalent saturated hydrocarbon group and the divalent saturated hydrocarbon group may be substituted with -O-, -S-, -CO-, or -NR'-.

R 'represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.]

[6] The colored curable resin composition according to [4], wherein the yellow azo dye is a compound represented by Formula (2).

Equation (2), Z ^1, Z ² and Z ³ is -CH ₂ respectively to even have a substituent independently represents a good divalent aliphatic hydrocarbon group having a carbon number of 1 to 16, contained in Z ^1, Z ² and Z ³ -May be substituted with -CO- or -O-. R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or a C1-C16 monovalent saturated aliphatic hydrocarbon group which may have a substituent or a C2-C18 acyl group which may have a substituent. A ¹ and A ² each independently represent a C6-C14 divalent aromatic hydrocarbon group which may have a substituent. B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent.]

[7] A color filter formed of the colored curable resin composition according to any one of [1] to [6].

[8] A display device comprising the color filter described in [7].

According to the colored curable resin composition of this invention, a high brightness blueish green color filter can be manufactured.

The colored curable resin composition of this invention contains a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D), and the said coloring agent (A) is a chlorinated phthalocyanine pigment ("pigment (P) ) "And yellow dye (it may be called" yellow dye (Y) "hereafter).

By using the coloring agent (A) containing the said yellow dye (Y) and pigment (P), the brightness of a color filter improves.

It is preferable that the colored curable resin composition of this invention contains a solvent (E) further.

In addition, the colored curable resin composition of this invention may contain at least 1 sort (s) chosen from the group which consists of a polymerization start adjuvant (D1) and surfactant (F) as needed.

In addition, in this specification, the compound illustrated as each component can be used individually or in combination of 2 types, unless a special understanding is requested | required.

<Coloring agent (A)>

The coloring agent (A) may contain a pigment (P) and a yellow dye (Y), and may also contain a pigment different from the pigment (P) (hereinafter may be referred to as "pigment (A2)").

Pigment (P) is preferably a pigment containing a compound represented by formula (P1).

[In formula (P1), a1, a2, a3 and a4 represent the integer of 0-4 independently of each other, and (a1 + a2 + a3 + a4) is 10 or more and 16 or less.]

In the pigment (P), the content of the compound represented by the formula (P1) is preferably at least 50 mass%, more preferably at least 70 mass%, even more preferably at least 90 mass%.

13 or more and 16 or less are preferable, and, as for (a1 + a2 + a3 + a4), 14 or more and 16 or less are more preferable.

As the pigment (P), C.I. Pigment green 7 and the like.

Pigment (P) may be subjected to rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound, atomization treatment by sulfuric acid atomization, or the like to remove impurities. Cleaning treatment with an organic solvent, water, or the like, removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

It is preferable that pigment P is uniform in particle size. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution can be obtained.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. You may use these pigment dispersants individually or in combination of 2 or more types. 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 CIBA Corporation), AJISPER (Ajinomoto) Fine Techno Co., Ltd., Disperbyk (manufactured by Beek Chemical Co., Ltd.), etc. are mentioned.

When using a pigment dispersant, the usage-amount is preferably 1 mass% or more and 100 mass% or less with respect to pigment (P), More preferably, they are 5 mass% or more and 50 mass% or less. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency for the pigment dispersion liquid of a uniform dispersion state to be obtained.

As for content of pigment (P), 1 mass% or more and 99 mass% or less are preferable with respect to the total amount of a coloring agent (A), 35 mass% or more and 99 mass% or less are more preferable, 40 mass% or more and 98 mass% or less desirable.

The yellow dye (Y) preferably has a maximum absorption wavelength in the range of 400 nm or more and 480 nm or less, more preferably in the range of 400 nm or more and 450 nm or less, still more preferably in the range of 410 nm or more and 435 nm or less. Have In addition, the maximum absorption wavelength can be calculated | required from the absorption spectrum which measured the solution which melt | dissolved dye in the solvent using the spectrophotometer, and it mentions later in detail.

Examples of the yellow dye (Y) include dyes classified as yellow dyes in the color index (published by The Society of Dyers and Colourists), and chemical structures such as azo dyes, metal complex dyes, quinoline dyes, acridine dyes, anthra Quinone dyes, naphthalimide dyes, nitro dyes, methine dyes, cyanine dyes and triphenylmethane dyes.

As the yellow dye (Y), for example, C.I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is described), 13, 14, 15, 19, 21, 23, 24, 25, 25: 1, 38, 62, 63, 68 79, 81, 82, 83, 83: 1, 88, 89, 90, 94, 98, 99, 151, 161, 162;

C.I. Acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 59, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 121, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138, 141;

C.I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 and the like.

Especially, as a yellow dye (Y), a yellow azo dye is preferable, For example, JP2009-13112-A, JP2009-13290-A, JP2009-13291-A, JP2009-13292-A, JP2009-13293-A, JP2009-280691 And dyes containing the compounds described in JP2009-299030-A, JP2010-1469-A, JP2010-275531-A, JP2010-275532-A, and JP2010-275533-A.

As for the said yellow azo dye, it is more preferable that it is a dye containing the compound represented by Formula (1).

[In Formula (1), A <^0> represents the C6-C14 bivalent aromatic hydrocarbon group which may have a substituent.

B <^0> represents the C6-C14 monovalent heterocyclic group which may have a substituent, and may have a C6-C14 monovalent aromatic hydrocarbon group or substituent.

R <^51> represents the C1-C18 acyl group which may have a hydrogen atom and a substituent, and may have a C1-C16 monovalent saturated hydrocarbon group or a substituent.

p1 represents 1 or 2. When p1 is 2, some A <^0> , B <^0> , R <^51> and R <^52> may mutually be same or different.

If p1 is 1, R ⁵² is, although a hydrogen atom or a substituent group represents a good monovalent saturated hydrocarbon group having 1 to 16 carbons, when p1 is 2, R ⁵² is even have a substituent divalent group having a carbon number of 1 to 35 The saturated hydrocarbon group may be represented and -CH ₂ -contained in the monovalent saturated hydrocarbon group and the divalent saturated hydrocarbon group may be substituted with -O-, -S-, -CO-, or -NR'-.

R 'represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.]

It is preferable that the compound represented by Formula (1) is a compound represented by Formula (2).

Equation (2), Z ^1, Z ² and Z ³ is -CH ₂ respectively to even have a substituent independently represents a good divalent aliphatic hydrocarbon group having a carbon number of 1 to 16, contained in Z ^1, Z ² and Z ³ -May be substituted with -CO- or -O-.

R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or a C1-C16 monovalent saturated aliphatic hydrocarbon group which may have a substituent or a C2-C18 acyl group which may have a substituent.

A ¹ and A ² each independently represent a C6-C14 divalent aromatic hydrocarbon group which may have a substituent.

B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent.]

Z ¹ , Z ² and Z ³ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent. Carbon number of a substituent is not contained in carbon number of a C1-C16 bivalent aliphatic hydrocarbon group, Preferably the number is 2-10, More preferably, it is 2-8.

Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include alkanediyl groups having 1 to 16 carbon atoms, and specifically, methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group and heptane. A diyl group, an octanediyl group, a decandiyl group, a tetradecanediyl group, and a hexadecanediyl group are mentioned.

-CH ₂ -in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with -CO- or -O-. The hydrogen atom contained in a C1-C16 aliphatic hydrocarbon group may be substituted by halogen atoms, such as a fluorine atom.

It is preferable that Z <^1> and Z <^2> may be a C1-C8 alkanediyl group which may contain -O-, and it is more preferable that it is a C5-C7 alkanediyl group which may contain -O-. Preferred groups include, for example,-(CH ₂ ) ₃ -,-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -,-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -And -CH ₂ -CH (CH ₃ )-.

It is preferable that Z <^3> is a C1-C8 divalent aliphatic hydrocarbon group which may contain -C (= C)-, It is more preferable that it is a C1-C8 unsubstituted alkanediyl group, It is C4-C8 It is more preferable that it is an unsubstituted alkanediyl group of. Preferred groups include-(CH ₂ ) ₂ -,-(CH ₂ ) ₄ -and -CH ₂ -C (= CH ₂ )-.

The C1-C16 monovalent saturated hydrocarbon group represented by R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be linear, branched or cyclic. Carbon number of a substituent is not contained in carbon number of the said saturated hydrocarbon group, Preferably it is C6-C10, More preferably, it is C1-C4.

Examples of the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and methylbutyl group (1, 1,3,3-tetramethylbutyl group etc.), methylhexyl group (1,5-dimethylhexyl group etc.), ethylhexyl group (2-ethylhexyl group etc.), cyclopentyl group, cyclohexyl group, methylcyclohexyl The actual group (2-methylcyclohexyl group etc.) and a cyclohexyl alkyl group are mentioned.

The hydrogen atom contained in a C1-C16 monovalent saturated hydrocarbon group may be substituted by the C1-C8 alkoxy group or carboxy group. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms include propoxypropyl group (3- (isopropoxy) propyl group and the like) and alkoxypropyl group (3- (2-ethylhexyloxy). ) Propyl group etc.) etc. are mentioned. As a C1-C16 aliphatic hydrocarbon group substituted by the carboxy group, 2- (carboxy) ethyl group, 3- (carboxy) propyl group, 4- (carboxy) butyl group, etc. are mentioned.

The divalent saturated hydrocarbon group having 1 to 35 carbon atoms for R ⁵² may be linear, branched or cyclic, and may be methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl or heptane. Diyl group, octanediyl group, decandiyl group, tetradecanediyl group, hexadecanediyl group, cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptandiyl group, cyclooctanediyl group , Cyclodecanediyl group, cyclotetradecanediyl group, cyclohexadecanediyl group, adamantanediyl group, and the like. Especially, it is preferable that it is linear or branched form.

-CH ₂ -in the divalent saturated hydrocarbon group having 1 to 35 carbon atoms may be substituted with -O-, -S-, -CO-, or -NR'-. The hydrogen atom contained in a C1-C35 divalent saturated hydrocarbon group may be substituted by halogen atoms, such as a fluorine atom.

As a C1-C6 monovalent aliphatic hydrocarbon group which shows R ', a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, etc. are mentioned.

The hydrogen atom contained in the C2-C18 acyl group which shows R <^51> , R <^53> and R <^54> may be substituted by the C1-C8 alkoxy group. The carbon number of the C2-C18 acyl group which may have a substituent includes the carbon number of a substituent, and the number is 6-10 preferably. As an acyl group which may have a substituent, an acetyl group, benzoyl group, a methoxy benzoyl group (p-methoxy benzoyl group etc.) etc. are mentioned, for example.

As R ⁵³ and R ⁵⁴ , a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and an acyl group having 2 to 5 carbon atoms are preferable. Preferred groups include, for example, hydrogen atoms, acetyl groups and propionyl groups.

As a C6-C14 bivalent aromatic hydrocarbon group which shows A <^0> , A <^1> and A <^2> , a phenylene group, a naphthalenediyl group, etc. are mentioned, Especially, a phenylene group is preferable.

As a substituent of a C6-C14 divalent aromatic hydrocarbon group, a halogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, a nitro group, a sulfo group, sulfamoyl group, N-substituted sulfamoyl group, etc. are mentioned. Can be.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom, a chlorine atom, and a bromine atom are preferable.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. An alkyl group is preferable, a C1-C2 alkyl group is more preferable, and a methyl group is especially preferable.

Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group. The C1-C4 alkoxy group is preferable, A C1-C2 alkoxy group is more preferable, A methoxy group is especially preferable.

As N-substituted sulfamoyl group, N-methyl sulfamoyl group, N-ethyl sulfamoyl group, N-propyl sulfamoyl group, N-isopropyl sulfamoyl group, N-butyl sulfamoyl group, N-isobutyl sulfamoyl group , N-sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamo Diary, 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-heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N N-1 substitution techniques such as-(2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group Pamoyl 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, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, etc. N-2 substituted sulfamoyl group, etc. are mentioned.

The N-substituted sulfamoyl group is preferably 1 to 16 carbon atoms, more preferably 4 to 16 carbon atoms.

B ⁰ , B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

A phenyl group, a naphthyl group, etc. are mentioned as a C6-C14 monovalent aromatic hydrocarbon group.

Examples of the monovalent heterocyclic group having 3 to 14 carbon atoms include the groups shown below.

[R represents a hydrogen atom or an organic group.]

Examples of the organic group include groups such as R ⁵⁹ described later.

The hydrogen atom contained in a C6-C14 monovalent aromatic hydrocarbon group and a C3-C14 monovalent heterocyclic group is a hydroxyl group, an oxo group, a C1-C16 monovalent aliphatic hydrocarbon group, a cyano group, an amino group, or N- It may be substituted with a substituted amino group.

As the N-substituted amino group, -NHR ⁵⁷ group and -NR ⁵⁷ R ⁵⁸ group are preferable. However, R ⁵⁷ and R ⁵⁸ each independently represent a C 1-16 monovalent saturated hydrocarbon group which may have a substituent or a C 3-14 monovalent heterocyclic group which may have a substituent. The group mentioned above is mentioned as a C1-C16 monovalent saturated hydrocarbon group and a C3-C14 monovalent heterocyclic group.

It is preferable that B <^1> and B <^2> are group of the same kind, and it is more preferable that A <^1> and A <^2> , R <^53> and R <^54> , Z <^1> and Z <^2> are group of the same kind, respectively. If it is these groups, manufacture of the compound represented by Formula (2) is easy.

It is preferable that B <^0> , B <^1> and B <^2> are group which is respectively independently represented by Formula (2-a).

[In formula (2-a), ^R59 represents the C1-C16 monovalent saturated hydrocarbon group which may have a hydrogen atom or a substituent. R ⁶⁰ represents a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.]

When the compound represented by formula (1) and the compound represented by formula (2) include the group represented by formula (2-a), these also include tautomers.

Examples of the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms include those mentioned above. R ⁵⁹ represents a methylbutyl group (1,1,3,3-tetramethylbutyl group, etc.), methylhexyl group (1,5-dimethylhexyl group, etc.), ethylhexyl group (2-ethylhexyl group, etc.), methylcyclo It is preferable that they are branched aliphatic hydrocarbon groups, such as a hexyl group (2-methylcyclohexyl group etc.) and an alkoxy propyl group (3- (2-ethylhexyloxy) propyl group etc.).

As a substituent of R <^59> and R <^60> , a hydroxyl group, a halogen atom, a C1-C8 alkoxy group, a C1-C8 acyloxy group, etc. are mentioned. The same thing as the above is mentioned as a C1-C8 alkoxy group. Examples of the acyloxy group having 1 to 8 carbon atoms include acetyloxy group, propionyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group and benzoyloxy group.

It is preferable that R ⁶⁰ is a methyl group.

As a compound represented by Formula (1), the compound of JP2010-275531-A is mentioned, Preferably, the compound represented by Formula (1-1)-Formula (1-10) is mentioned. In the table, A ¹ , A ² , Z ¹ and Z ² indicate the number of bonds on the side closer to Z ³ in the number of bonds on the right side.

The compound represented by Formula (2) can be manufactured by the method of JP2010-275531-A.

Content of yellow dye (Y) is 1 mass% or more and 65 mass% or less with respect to the total amount of a coloring agent (A), and 2 mass% or more and 55 mass% or less are preferable.

The said coloring agent (A) may also contain pigment (A2) with a pigment (P) and a yellow dye (Y).

Examples of the pigment (A2) include compounds classified as pigments in the color index (Published by The Society of Dyers and Colurists). Especially, it is a yellow pigment and a green pigment.

As a yellow pigment, for example, C.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, 173, 194, 214 and the like, and the yellow pigments described in JP2001-354869-A and JP2007-224176-A.

As a green pigment, C.I. Pigment green 36, 58, etc. are mentioned.

Among these, as pigment (A2), C.I. Pigment yellow 138, 139, 150; C.I. Pigment Greens 36 and 58 are preferred. By including these pigments, optimization of the transmission spectrum is easy, and chemical resistance becomes favorable. These pigments may be used alone or in combination of two or more.

Pigment (A2) may be subjected to rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound or the like, or an atomization treatment by sulfuric acid atomization or the like to remove impurities. Cleaning treatment with an organic solvent, water, or the like, removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

It is preferable that pigment (A2) has a uniform particle size. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution can be obtained. The pigment (P) and the pigment (A2) may be mixed and then dispersed together.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. You may use these pigment dispersants individually or in combination of 2 or more types. 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 CIBA), AJISPER (Ajinomoto) Fine Techno Co., Ltd., Disperbyk (manufactured by Beek Chemical Co., Ltd.), etc. are mentioned.

When using a pigment dispersant, the usage-amount is preferably 1 mass% or more and 100 mass% or less with respect to pigment (A2), More preferably, they are 5 mass% or more and 50 mass% or less. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency which can obtain the pigment dispersion liquid of a uniform dispersion state.

When it contains a pigment (A2), 1 mass%-90 mass% are preferable in a coloring agent (A), and 3 mass%-80 mass% are more preferable. By setting it as such a ratio, optimization of a transmission spectrum becomes easy and the color filter obtained tends to be excellent in contrast, lightness, heat resistance, and chemical resistance.

When a coloring agent (A) consists of a pigment (P) and a yellow dye (Y), these content is each with respect to the total amount of a coloring agent (A),

Pigment (P); 35 mass% or more and 99 mass% or less

Yellow dye (Y); 1 mass% or more and 65 mass% or less are preferable,

Pigment (P); 40 mass% or more 98 mass% or less

Yellow dye (Y); 2 mass% or more and 55 mass% or less are more preferable.

When the coloring agent (A) contains the pigment (A2), the content of the pigment (P), the yellow dye (Y) and the pigment (A2) is, respectively, relative to the total amount of the coloring agent (A),

Pigment (P); 5 mass% or more 98 mass% or less

Yellow dye (Y); 1 mass% or more and 65 mass% or less

Pigment (A2); 1 mass% or more and 90 mass% or less are preferable,

Pigment (P); 9 mass% or more and 97 mass% or less

Yellow dye (Y); 2 mass% or more and 55 mass% or less

Pigment (A2); 1 mass% or more and 85 mass% or less are more preferable.

Content of a coloring agent (A) becomes like this. Preferably it is 5 mass%-70 mass% with respect to solid content in colored curable resin composition, More preferably, it is 8 mass%-60 mass%, More preferably, it is 10 mass%-57 mass%. %to be. Here, solid content means the sum total of the component except the solvent in colored curable resin composition. When the content of the colorant (A) is in the above-described range, a desired spectral or color concentration can be obtained when the color filter is used, and a necessary amount of resin or a polymerizable compound can be contained in the composition. Can be formed.

<Resin (B)>

Although resin (B) is not specifically limited, It is preferable that it is alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to resin [K6].

At least one selected from the group consisting of resin [K1] unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter may be referred to as "(a)"), a cyclic ether structure having 2 to 4 carbon atoms, and Copolymer with monomer (b) (hereinafter sometimes referred to as "(b)") having an ethylenically unsaturated bond;

Monomer (c) copolymerizable with resin [K2] (a) and (b) and (a) (however different from (a) and (b)) (hereinafter may be referred to as "(c)") Copolymers with;

Copolymer of resin [K3] (a) and (c);

Resin [K4] Resin which (b) was made to react with the copolymer of (a) and (c);

Resin [K5] Resin which (a) was made to react with the copolymer of (b) and (c);

Resin [K6] Resin which (a) was made to react with the copolymer of (b) and (c), and carboxylic anhydride was made to react.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic 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, 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- N, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups such as cyclo [2.2.1] hept-2-ene and 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-tetrahydrophthalic anhydride Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl of divalent or more polyvalent carboxylic acid, such as succinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] Esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid.

Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable from the point of copolymerization reactivity or the solubility in aqueous alkali solution.

In addition, in this specification, "(meth) acryloyl" shows at least 1 sort (s) chosen from the group which consists of acryloyl and methacryloyl. Notation, such as "(meth) acrylic acid" and "(meth) acrylate", has the same meaning.

(b) is a polymeric compound which has an ethylenically unsaturated bond with a C2-C4 cyclic ether structure (for example, at least 1 sort (s) chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring). As for (b), the monomer which has a C2-C4 cyclic ether structure and a (meth) acryloyloxy group is preferable.

In addition, in this specification, "(meth) acrylic acid" shows at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", has the same meaning.

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)") and a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter "( b2) ", and the monomer (b3) which may have a tetrahydrofuryl group and ethylenically unsaturated bond (Hereinafter, it may be called" (b3) ").

(b1) is a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized and an unsaturated alicyclic hydrocarbon are epoxidized. The monomer (b1-2) (henceforth "(b1-2)" may be mentioned) which has a given structure is mentioned.

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and o-vinyl benzyl. 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 (glycidyloxy Methyl) 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 have.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., CELLOXIDE 2000; manufactured by Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth ) Acrylic (for example, CYCLOMER A400; manufactured by Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER M100; manufactured by Daicel Chemical Co., Ltd.), formula ( The compound represented by I), the compound represented by Formula (II), etc. are mentioned.

[In Formula (I) and Formula (II), R <^b1> and R <^b2> represent a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ^b1 and X ^b2 represent a single bond, -R ^b3- , * -R ^b3 -O-, * -R ^b3 -S- or * -R ^b3 -NH-.

R ^b3 represents a C1-C6 alkanediyl group.

* Represents the number of bonds 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.

As an alkyl group in which a hydrogen atom was substituted by hydroxy, it is a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. 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.

Examples of the alkanediyl group are 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-1, 6-diyl group etc. are mentioned.

X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- or * -CH ₂ CH ₂ -O-, and more preferably a single bond or * -CH ₂ CH ₂ -O- (* represents the number of bonds with O).

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

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

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone, or may be mixed and used at any ratio. When used by mixing, the content ratio of the compound represented by formula (I) and the compound represented by formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 90: on a molar basis. 10, More preferably, it is 20: 80-80: 20.

As a monomer (b2) which has an oxetanyl group and ethylenically unsaturated bond, the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxy ethyl oxetane, 3-ethyl-3- acryloyloxy ethyl oxetane, etc. are mentioned.

As a monomer (b3) which has a tetrahydrofuryl group and ethylenically unsaturated bond, the monomer which has 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 Yuki Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

It is preferable that (b) is (b1) from the point that reliability, such as heat resistance and chemical-resistance, of a color filter obtained can be made higher. Moreover, (b1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

As (c), for example, 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-methylcyclo Hexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (common name in the art is called "dicyclopentanyl (meth) acrylate." , May be referred to as "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (as the common name in the art, "dicyclopentenyl (Meth) acrylates are called), dicyclo Tanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naph (Meth) acrylic acid esters such as methyl (meth) acrylate and 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, and diethyl itaconate;

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 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- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclo-unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, etc. are preferable at the point of copolymerization reactivity and heat resistance.

In resin [K1], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K1],

structural unit derived from (a); 2 ~ 60 mol%

structural unit derived from (b); It is preferable that it is 40-98 mol%,

structural unit derived from (a); 10-50 mol%

structural unit derived from (b); It is more preferable that it is 50-90 mol%.

When the ratio of the structural unit of resin [K1] exists in the said range, there exists a tendency which is excellent in the storage stability of colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance of the obtained colored pattern.

Resin [K1] is, for example, the method described in the document "Experimental method of polymer synthesis" (Okasu Takayuki, published by Hakoko Sho Chemical Co., First Edition, March 1, 1972) and the citations described in this document. It can manufacture by reference.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are put in a reaction vessel, and the method of heating and keeping warm while stirring and deoxygenating by replacing oxygen with nitrogen, for example, Can be mentioned. In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, What is normally used in this field can be used. For example, an azo compound (2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.) and an organic peroxide (benzoyl peroxide etc.) are mentioned as a polymerization initiator. As a solvent, what is necessary is just to melt | dissolve each monomer, and the solvent (E) mentioned later as a solvent of colored curable resin composition is mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may remove what was taken out as solid (powder) by methods, such as reprecipitation. In particular, by using the solvent (E) mentioned later as a solvent at the time of this superposition | polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

In resin [K2], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K2],

structural unit derived from (a); 2 to 45 mol%

structural unit derived from (b); 2 ~ 95 mol%

structural unit derived from (c); It is preferable that it is 1-65 mol%,

structural unit derived from (a); 5-40 mol%

structural unit derived from (b); 5 to 80 mol%

structural unit derived from (c); It is more preferable that it is 5-60 mol%.

When the ratio of the structural unit of resin [K2] exists in the above-mentioned range, there exists a tendency which is excellent in the storage stability of the colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the obtained colored pattern. .

Resin [K2] can be manufactured by the same method as the method described as a manufacturing method of resin [K1], for example.

In resin [K3], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K3],

structural unit derived from (a); 2 ~ 60 mol%

structural unit derived from (c); It is preferable that it is 40-98 mol%,

structural unit derived from (a); 10-50 mol%

structural unit derived from (c); It is more preferable that it is 50-90 mol%.

 Resin [K3] can be manufactured by a method similar to the method described as a manufacturing method of resin [K1], for example.

Resin [K4] obtains the copolymer of (a) and (c), and adds the C2-C4 cyclic ether which (b) has to carboxylic acid and / or carboxylic anhydride which (a) has It can manufacture.

First, the copolymer of (a) and (c) is manufactured by the method similar to the method described as a manufacturing method of resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the ratio similar to what was illustrated by resin [K3].

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of carboxylic acid and / or carboxylic anhydride derived from (a) in the said copolymer.

Subsequent to the preparation of the copolymer of (a) and (c), the atmosphere in the flask was replaced by nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride with a cyclic ether (e.g. tris (dimethyl Aminomethyl) phenol and the like) and a polymerization inhibitor (for example, hydroquinone and the like) and the like can be put in a flask, and the resin [K4] can be produced by, for example, reacting at 60 to 130 ° C. for 1 to 10 hours.

As for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of the storage stability of colored curable resin composition, the developability at the time of forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the pattern obtained to become favorable. Since the reactivity of cyclic ether is high and it is hard to remain unreacted (b), as (b) used for resin [K4], (b1) is preferable and (b1-1) is more preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b) and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b) and (c).

Reaction conditions, such as a preparation method, reaction temperature, and time, can be adjusted suitably in consideration of a manufacturing facility, the calorific value by polymerization. On the other hand, similarly to the polymerization conditions, the preparation method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

Resin [K5] is a 1st step and obtains the copolymer of (b) and (c) in the same way as the manufacturing method of resin [K1] mentioned above. In the same manner as described above, the obtained copolymer may be used as it is, the concentrated or diluted solution may be used, or the obtained copolymer may be used as a solid (powder) by reprecipitation or the like.

It is preferable that the ratio of the structural unit derived from (b) and (c) exists in the following ranges with respect to the total number of moles of all the structural units which comprise said copolymer.

structural unit derived from (b); 5 to 95 mol%

structural unit derived from (c); It is preferable that it is 5-95 mol%,

structural unit derived from (b); 10 to 90 mol%

structural unit derived from (c); It is more preferable that it is 10-90 mol%.

Moreover, the carboxylic acid or carboxylic anhydride which (a) has in the cyclic ether derived from (b) which the copolymer of (b) and (c) has on the conditions similar to the manufacturing method of resin [K4] Resin [K5] can be obtained by making it react.

As for the usage-amount of (a) made to react with said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (b), as (b) used for resin [K5], (b1) is preferable and (b1-1) is more preferable.

Resin [K6] is resin which made carboxylic anhydride further react with resin [K5].

The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride.

Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -Tetrahydrophthalic anhydride, dimethyl tetrahydrophthalic anhydride, 5, 6- dicarboxy bicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), etc. are mentioned. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid. Resins such as coalescing [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 ] decylacrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decylacrylate / (meth) acrylic acid / vinyltoluene / dicyclophene Resins such as tenyl (meth) acrylate copolymer and 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; Resin which glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer, and glycidyl (meth) to the tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin [K4], such as resin which added the acrylate, and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Resins [K5], such as resin which made (meth) acrylic acid react with the copolymer; Resin [K6], such as resin which further made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, is mentioned. .

Especially, as resin (B), resin [K1], resin [K2], and resin [K3] are preferable.

The weight average molecular weight of polystyrene conversion of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is in the above-described range, the coating film hardness is improved, the residual film ratio is also high, the solubility in the developer of the unexposed part is good, and the resolution tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of resin (B) becomes like this. Preferably it is 50-170 mg-KOH / g, More preferably, it is 60-150 mg-KOH / g, More preferably, it is 70-135 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to solid content of colored curable resin composition, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When content of resin (B) exists in the said range, there exists a tendency for the solubility to the developing solution of an unexposed part to be high.

<Polymeric Compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by active radicals and / or acids generated from the polymerization initiator (D) by the action of light or heat, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Preferably, a (meth) acrylic acid ester compound is mentioned.

It is preferable that it is a polymeric compound which has 3 or more of ethylenically unsaturated bonds as said polymeric compound (C). Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tripenta Erythritol octa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acrylic Loyloxyethyl) 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, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned. Especially, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

Content of polymeric compound (C) becomes like this. Preferably it is 7-65 mass% with respect to solid content of colored curable resin composition, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When content of the said polymeric compound (C) exists in the said range, since hardening arises enough, the film thickness ratio before and behind image development improves, it becomes difficult to undercut into a pattern, and adhesiveness tends to become favorable, and it is preferable. .

<Polymerization Initiator (D)>

As the polymerization initiator (D), any compound capable of generating an active radical, an acid or the like by the action of light or heat to start the polymerization can be used, and any known polymerization initiator can be used.

Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds, biimidazole compounds, and the like.

The 0-acyl oxime compound is a compound having a partial structure represented by formula (d1).

Hereinafter, * represents a bond number.

Examples of the O-acyl oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-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-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentyl propane-1-one-2-imine, etc. are mentioned. You may use commercially available products, such as IRGACURE (trademark) OXE01, OXE02 (above BASF Corporation), and N-1919 (ADEKA Corporation).

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.

Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4- Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1 -On etc. can be mentioned. You may use commercially available products, such as IRGACURE (trademark) 369, 907, and 379 (above, BASF Corporation make).

Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxy Oxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, (alpha)-diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

In terms of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by formula (d2) is preferable.

Examples of the triazine compound 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 (trichloro To methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) Tenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -[2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

2,4,6-trimethyl benzoyl diphenyl phosphine oxide etc. are mentioned as an acyl phosphine oxide compound. You may use commercially available products, such as IRGACURE 819 (made by BASF Corporation).

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 (see eg JP6-75372-A, JPH06-75373-A, etc.), 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, eg, JPS48-38403-B, JPH62-174204-A, etc.), the phenyl group at the 4,4 ', 5,5'-position already substituted by a carboalkoxy group And a dazole compound (for example, see JPH07-10913-A and the like).

As the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization start adjuvant (D1) (especially amines) mentioned later.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4- Acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, diphenyl iodine Onium salts, such as nium hexafluoro antimonate, nitrobenzyl tosylate, benzoin tosylate, etc. are mentioned.

As a polymerization initiator (D), the polymerization initiator containing at least 1 sort (s) chosen from the group which consists of an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound is preferable, and O- The polymerization initiator containing an acyl oxime compound is more preferable, and the polymerization initiator containing an O-acyl oxime compound and an alkylphenone compound is more preferable.

Content of a polymerization initiator (D) becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), More preferably, it is 5-25 mass parts. When content of a polymerization initiator (D) exists in the said range, it exists in the tendency which can form a pattern with high sensitivity and can obtain a color filter of high brightness.

The polymerization start aid (D1) may be further included together with the polymerization initiator (D). A polymerization start adjuvant (D1) is a compound or sensitizer used in order to accelerate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization started with a polymerization initiator.

An amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound etc. are mentioned as a polymerization start adjuvant (D1).

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoic acid. 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4 ' -Bis (ethylmethylamino) benzophenone etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercially available products, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxy Anthracene, 2-ethyl-9, 10-dibutoxy anthracene, etc. are mentioned.

As the thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxythioke Santon etc. can be mentioned.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Diphenylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

As a polymerization start adjuvant (D1), a thioxanthone compound is preferable.

In addition, when using a polymerization start adjuvant (D1), the usage-amount becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), More preferably, it is 1-20 mass It is wealth. Moreover, it is 20-100 mass parts with respect to 100 mass parts of content of a polymerization initiator (D), More preferably, it is 30-80 mass parts. When the amount of the polymerization initiation assistant (D1) is in this range, a pattern can be formed with high sensitivity, and there is a tendency to obtain a higher color filter.

&Lt; Solvent (E) >

Solvent (E) is not specifically limited, The solvent normally used in the field | area can be used. For example, ester solvent (solvent containing -COO-), ether solvent other than ester solvent (solvent containing 0-), ether ester solvent (solvent containing -COO- and -O-), ester solvent other than Ketone solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

As said ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexanol acetate, gamma -butyrolactone, and the like.

As said 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 dibutyl ether, anisole, phentol, methyl anisole Etc. can be mentioned.

As said ether ester solvent, methyl methoxy acetate, methoxy acetate, methoxy acetate, ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Tate, di, and the like ethylene glycol monobutyl ether acetate.

As said ketone solvent, 4-hydroxy-4-methyl- 2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl- 2-pentanone, cyclo Pentanone, cyclohexanone, isophorone, etc. are mentioned.

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

Benzene, toluene, xylene, mesitylene, etc. are mentioned as said aromatic hydrocarbon solvent.

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

Among the solvents described above, organic solvents having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm (101.325 kPa) are preferable from the viewpoint of applicability and dryness. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxy Butyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, etc. are preferable, and propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether , Dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate are more preferable.

Content of the solvent (E) in colored curable resin composition becomes like this. Preferably it is 70-95 mass% with respect to colored curable resin composition, More preferably, it is 75-92 mass%. In other words, solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass%, More preferably, it is 8-25 mass%. When content of a solvent (E) exists in the said range, flatness at the time of application | coating becomes favorable, and since a color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

<Surfactant (F)>

As surfactant (F), silicone type surfactant, a fluorine-type surfactant, the silicone type surfactant which has a fluorine atom, etc. are mentioned. These may have a polymeric group in a side chain.

As said silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, Toray silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340 And KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, Florade (brand name) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), mecha park (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30, copper RS -718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (manufactured by Misubishima Terry Alden Shigasei Co., Ltd.), Suplon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemicals Co., Ltd.), and the like.

As silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, Mega Park (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by DIC Corporation), and the like.

Content of surfactant (F) becomes like this. Preferably it is 0.001 mass% or more and 0.2 mass% or less with respect to colored curable resin composition, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably, it is 0.01 mass% or more and 0.05 mass% It is as follows. However, content of the said pigment dispersant is not contained in content of the said surfactant (F). If content of surfactant (F) exists in the said range, flatness of a coating film can be made favorable.

&Lt; Other components >

The colored curable resin composition of this invention may contain various additives, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, as needed.

<The manufacturing method of colored curable resin composition>

The colored curable resin composition of this invention is a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), and a polymerization start adjuvant (D1), a solvent (E) used as needed, It can prepare by mixing surfactant (F) and other components.

Pigment (P) is previously mixed with a solvent (E), and it is preferable to disperse | distribute using a bead mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. At this time, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. In the obtained pigment dispersion liquid, yellow dye (Y), the remainder of resin (B), and a polymeric compound (C), and the remainder of the polymerization initiator (D), the solvent (E) used as needed, surfactant (F), and The target colored curable resin composition can be prepared by mixing other components to a predetermined concentration.

The yellow dye (Y) may be dissolved in the solvent (E) in advance to prepare a solution. It is preferable to filter this solution with the filter of about 0.01-1 micrometer in diameter.

It is preferable to filter the colored curable resin composition mixed and prepared as mentioned above with the filter of about 0.1-10 micrometers in diameter.

<Color filter>

The colored curable resin composition of the present invention is useful for producing a bluish green color filter. The bluish green color filter preferably has a CIE chromaticity coordinate in a C light source, a 2-degree field of view, for example, in the range of 0.140≤x≤0.270, 0.500≤y≤0.690, more preferably 0.170≤X≤0.260, 0.500 In the range of ≤ y ≤ 0.680, more preferably in the range of 0.200 ≤ x ≤ 0.250, 0.550 ≤ y ≤ 0.680, a high brightness blue light green color filter can be obtained.

As a method of manufacturing the coloring pattern of a color filter with the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable. The photolithographic method is a method of applying the colored curable resin composition to a substrate, drying to form a composition layer, and exposing and developing the composition layer through a photomask. In the photolithography method, the colored coating film which is the hardened | cured material of the said composition layer can be formed by not using a photomask and / or developing at the time of exposure.

The film thickness of the produced color filter is not specifically limited, It can adjust suitably according to the objective, a use, etc., for example, 0.1-30 micrometers, Preferably it is 1-20 micrometers, More preferably, it is 1-6 micrometers.

As a board | substrate, glass plates, such as quartz glass, borosilicate glass, alumina silicate glass, and the soda-lime glass which silica-coated the surface, resin plates, such as polycarbonate, polymethyl methacrylate, and a polyethylene terephthalate, silicon, aluminum on the said board | substrate, Silver and the thing which formed the silver / copper / palladium alloy thin film etc. are used. Separate color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

Formation of each color pixel by the photolithographic method can be carried out under known or conventional conditions or conditions. For example, it can manufacture by the following formula.

First, a coloring curable resin composition is apply | coated on a board | substrate, heat-drying (prebaking) and / or drying under reduced pressure, remove volatile components, such as a solvent, and dry, and obtain a smooth composition layer.

As a coating method, a spin coat method, the slit coat method, the slit & spin coat method, etc. are mentioned.

30-120 degreeC is preferable and, as for the temperature at the time of heat-drying, 50-110 degreeC is more preferable. Moreover, it is preferable that it is for 10 seconds-60 minutes, and, as for heating time, it is more preferable that it is for 30 seconds-30 minutes.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

The film thickness of a composition layer is not specifically limited, It can adjust suitably according to the film thickness of the target color filter.

The composition layer is then exposed through a photomask for forming the desired colored pattern. The pattern on this photomask is not specifically limited, The pattern according to the intended use is used.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light of less than 350 nm may be cut using a filter that cuts the wavelength region, or light around 436 nm, 408 nm, or 365 nm may be selectively cut using a bandpass filter that extracts the wavelength range. It may take out. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

Since it is possible to irradiate parallel light rays uniformly to the entire exposure surface or to accurately position the photomask and the substrate, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

A coloring pattern is formed on a board | substrate by developing the composition layer after exposure contacting with a developing solution. The unexposed part of a composition layer melt | dissolves in a developing solution and is removed by image development. As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developing solution may contain surfactant.

The developing method may be any of a puddle method, a dipping method and a spray method. In addition, during development, the substrate may be tilted at an arbitrary angle.

It is preferable to wash with water after image development.

Furthermore, it is preferable to post-bake on the obtained coloring pattern. 150-250 degreeC is preferable and, as for post-baking temperature, 160-235 degreeC is more preferable. 1-120 minutes are preferable and, as for post-baking time, 10 to 60 minutes are more preferable.

The coloring pattern and colored coating film obtained in this way are useful as a color filter.

According to the colored curable resin composition of this invention, since a blue light green color filter of especially high brightness can be manufactured, this color filter is a display device (for example, a liquid crystal display device, an organic EL device, etc.), an electronic paper, a solid. It is useful as a color filter used for an imaging element.

Example

Next, an Example is given and this invention is demonstrated further more concretely. "%" And "part" in an example are mass% and a mass part, unless there is particular notice.

Synthesis Example 1

200 parts of water were added to 10 parts of m-toluidine-4-sulfonic acid (compound represented by Formula (a-2)), and it adjusted to pH 7-8 with 30% sodium hydroxide aqueous solution under ice-cooling. The following operation was performed under ice cooling. 11.1 parts of sodium nitrite were added, and it stirred for 30 minutes. 39 parts of 35% hydrochloric acid was added little by little to make a brown solution, and it stirred for 2 hours. The aqueous solution which melt | dissolved 10.1 parts of amic sulfuric acid in 101 parts of water was added to the reaction solution, and it stirred, and obtained the suspension containing a diazonium salt.

125 parts of water and N-methyl in 14 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrido-2-one (compound represented by formula (c-2)) After adding 25 parts of pyrrolidone, it adjusted to pH 8-9 with 30% sodium hydroxide aqueous solution under ice cooling.

The following operation was performed under ice cooling. After stirring the said pyridone aqueous solution to make it a colorless solution, the suspension containing diazonium salt was dripped over 2 hours, adjusting pH to 8-9 with 30% sodium hydroxide aqueous solution. After completion of dropping, a yellow suspension was obtained by further stirring for 2 hours. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 21.4 parts (yield 87%) of compounds which are represented by a formula (d-3) were obtained.

0.35 g of compound (d-3) was dissolved in N, N-dimethylformamide to a volume of 250 cm 3, of which 2 cm 3 was diluted with water to a volume of 100 cm 3 (concentration: 0.028 g / L), and spectroscopy. Absorption spectra were measured using a photometer (quartz cell, optical path length; 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λ max = 433 nm.

To a flask equipped with a cooling tube and a stirring device, 5.0 parts of compound (d-3), 35 parts of acetonitrile and 1.6 parts of N, N-dimethylformamide were added, and thionyl chloride 2.4 was maintained at 20 ° C. or lower while stirring. Wealth was added and added. After completion | finish of dripping, it heated up at 40 degreeC, hold | maintained and reacted for 2 hours at the same temperature, and cooled at 20 degreeC after that. The reaction solution after cooling was poured with stirring into 150 parts of ice water, followed by stirring for 30 minutes. The precipitated yellow crystals were separated by filtration, washed well with tap water, and dried under reduced pressure at 60 ° C for 2 hours. A flask equipped with a cooling tube and a stirring device was separately prepared, and 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone were added thereto, and the yellow crystal adjusted above was kept while maintaining the temperature below 20 ° C under stirring. It was put in for 1 hour. After adding yellow crystals, the liquid temperature was raised to room temperature, and then the reaction solution was stirred for 30 minutes. 40 parts of methanol was added to the reaction solution, and the mixture was stirred. Then, the mixed solution was added to the mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.9 parts (yield 69%) of the compound represented by formula (III-3).

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

The following reaction was performed in nitrogen atmosphere. After adding 150 parts of N-methylpyrrolidone to 49.9 parts of compound (III-3), it stirred for 30 minutes and adjusted the reaction solution. 6.8 parts of sebacic acid chlorides were dripped under room temperature, stirring the reaction solution. After completion of the dropwise addition, the mixture was further stirred for 8 hours. 7.8 parts of adipic acid chlorides were dripped. After completion of the dropwise addition, the mixture was further stirred for 8 hours. The reaction solution was poured into 300 parts of water, 80 parts of ethyl acetate was added, and the mixture was stirred for 30 minutes.

After separating an organic phase using the separating funnel, it wash | cleaned further with 500 parts of water, 3000 parts of 10% sodium carbonate aqueous solution, 1000 parts of 10% acetic acid aqueous solution, and 1000 parts of ion-exchange water.

The organic phase separated from the solvent was distilled off, and 2.0 parts of dye (a) which was a mixture of the compound represented by Formula (1-6) and the compound represented by Formula (1-7) was obtained. Yield 85%.

0.35 g of dye (A) was dissolved in ethyl lactate to make a volume of 250 cm 3, of which 2 cm 3 was diluted with ion-exchanged water to a volume of 100 cm 3 (concentration: 0.028 g / L), and a spectrophotometer (quartz cell) , Optical path length; 1 cm). This compound showed an absorbance of 2.2 (arbitrary unit) at λ max = 431 nm.

<Measurement of the content ratio in the mixture>

The content ratio of the compound represented by Formula (1-6) and the compound represented by Formula (1-7) in dye (a) was measured by the analytical curve method using high performance liquid chromatography (HPLC). The calibration curve method is a method of determining an unknown concentration from a concentration-absorbance relationship of a standard solution column of a known concentration in determining a concentration of a substance in a solution.

HPLC apparatus Prominence (manufactured by Shimadzu Seisakusho)

Liquid feeding unit: 2 LC-20AT

Auto sampler: 1 SIL-20A

Column Oven: 1 unit CTO-20A

UV detector: 1 SPD-20A

On-line degasser: 1 DGU-20A

Column Wakosil II 3C18HG (3 μm, 3 mmφ × 150 mm)

Mobile phase A solution; 0.1% TBAB / water: acetonitrile (9: 1)

B liquid; 0.1% TBAB / water: acetonitrile (1: 9)

Gradient (B liquid)

B initial concentration 25%

25% → (30 minutes) → 100% (hold for 20 minutes)

Detection wavelength 254 nm

Column temperature 40 ℃

0.5 mL / min flow

Injection volume 5 μL

TBAB: tetrabutylammonium bromide

The compound represented by Formula (1-6) and the compound represented by Formula (1-7) were dissolved in acetonitrile, respectively, and the solution of the density | concentration shown in Table 11 was adjusted. About this solution, the high performance liquid chromatography analysis was performed on the conditions mentioned above, and the elution time and peak area were measured.

The results are shown in Table 11.

From the concentration of the solution and the measured peak area, the calibration curve was calculated by the following formula

Calibration curve of the compound represented by formula (1-6): (peak area) = 72.2 x (concentration)

Calibration curve of the compound represented by formula (1-7): (peak area) = 76.0 x (concentration)

13.9 mg of the dye (A) was dissolved in acetonitrile to have a volume of 50 cm 3 (concentration: 0.278 g / L), followed by high performance liquid chromatography analysis under the above conditions, and the elution time and peak area were measured. The compound represented by Formula (1-7) was eluted at the elution time 35.9 minutes, and the peak area was 944436. The compound represented by Formula (1-6) was eluted at an elution time of 37.9 minutes, and its peak area was 1108707.

When the content ratio of each compound in dye (a) was calculated | required using said analytical curve, it was compound = 44.7 / 55.3 represented by compound represented by Formula (1-6) / formula (1-7).

Synthesis Example 2

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was heated to 70 ° C while stirring.

Next, 60 parts by mass of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) are molar ratios of 50: It melt | dissolved in 240 mass parts and 140 mass parts of ethyl lactates, the solution was prepared, and this melt solution was dripped at the flask kept at 70 degreeC over 4 hours using the dropping funnel.

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of ethyl lactates was dripped in the flask over 4 hours using the other dropping funnel. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1 x 10 ³ , the molecular weight distribution was 2.1, the solid content was 26 mass%, the solid acid value. A 120 mg-KOH / g resin B1 solution was obtained. Resin B1 has the following structural unit.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis example was performed on condition of the following using GPC method.

Device; K2479 (manufactured by Shimadzu Seisakusho Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detectors; RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution.

Example 1

[Preparation of colored curable resin composition]

(A) Colorant: C.I. Pigment green 7 (pigment) 38 parts

Acrylic pigment dispersant 17 parts

Propylene glycol monomethyl ether acetate 245 parts

A pigment dispersion in which the pigments were mixed and the pigment was sufficiently dispersed using a bead mill,

(A) Colorant: 38 parts of dyes (a) (yellow dyes)

(B) Resin: Resin B1 (Solid Content) 40 Parts

(C) Polymerizable Compound: dipentaerythritol hexaacrylate

(KAYARAD DPHA; Nihon Kayaku Co., Ltd.) 60 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine

(IRGACURE OXE 01; manufactured by BASF Corporation) 10 parts

(F) Leveling agent: polyether modified silicone oil

(Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.12part

(E) Solvent: 261 parts of ethyl lactate

(E) Solvent: Propylene glycol monomethyl ether acetate 424 parts

Was mixed to obtain a colored curable resin composition.

[Production of colored pattern]

After apply | coating the said colored curable resin composition on the 2 inch square glass substrate (Eagle XG; Corning Corporation make) by the spin coat method, it prebaked at 100 degreeC for 3 minutes, and formed the composition layer. After cooling, the distance between the substrate on which the composition layer was formed and the quartz glass photomask was set to 200 µm, and an exposure dose of 40 mJ / cm 2 was used under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). Light emission at 365 nm). On the other hand, as a photomask, the thing in which the 100-micrometer line & space pattern was formed was used. The composition layer after light irradiation was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 60 seconds and developed. After washing with water, coloring was carried out in an oven for 20 minutes post-baking at 230 ° C. A pattern was obtained.

[Film thickness measurement]

About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nihon Shinkugi Jutsu Co., Ltd. product). The results are shown in Table 12.

[Color evaluation]

About the obtained coloring pattern, spectroscopic measurement was carried out using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) in the XYZ colorimeter of the CIE using the characteristic function of the C light source. And brightness Y was measured. The results are shown in Table 12.

Example 2

(A) Colorant: 43 parts of Pigment Green 7 (pigment)

Acrylic pigment dispersant 19 parts

Propylene glycol monomethyl ether acetate 272 parts

A pigment dispersion in which the pigments were mixed and the pigment was sufficiently dispersed using a bead mill,

(A) Colorant: C.I. Pigment yellow 138 (pigment) 17 copies

5.1 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 86 parts

A pigment dispersion in which the pigments were mixed and the pigment was sufficiently dispersed using a bead mill,

(A) Colorant: 26 parts of dyes (a) (yellow dyes)

(B) Resin: Resin B1 (Solid Content) 40 Parts

(C) Polymerizable Compound: dipentaerythritol hexaacrylate

(KAYARAD DPHA; Nihon Kayaku Co., Ltd.) 60 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine

(IRGACURE OXE 01; manufactured by BASF Corporation) 10 parts

(F) Leveling agent: polyether modified silicone oil

(Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.13part

(E) Solvent: 256 parts of ethyl lactate

(E) Solvent: Propylene glycol monomethyl ether acetate 386 parts

Was mixed to obtain a colored curable resin composition.

The coloring pattern was produced by operation similar to Example 1, and the film thickness measurement and chromaticity evaluation were performed.

The results are shown in Table 12.

Example 3

[Preparation of colored curable resin composition]

(A) Colorant: C.I. Pigment green 7 (pigment) 44 copies

20 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 273 parts

A pigment dispersion in which the pigments were mixed and the pigment was sufficiently dispersed using a bead mill,

(A) Colorant: C.I. Pigment yellow 138 (pigment) 26 copies

7.8 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 129 parts

A pigment dispersion in which the pigments were mixed and the pigment was sufficiently dispersed using a bead mill,

(A) Colorant: Dye (A) (Yellow Dye) 18 parts

(B) Resin: Resin B1 (Solid Content) 40 Parts

(C) Polymerizable Compound: dipentaerythritol hexaacrylate

(KAYARAD DPHA; Nihon Kayaku Co., Ltd.) 60 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine

(IRGACURE OXE 01; manufactured by BASF Corporation) 10 parts

(F) Leveling agent: polyether modified silicone oil

(Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.14part

(E) Solvent: 252 parts of ethyl lactate

(E) Solvent: Propylene glycol monomethyl ether acetate 353 parts

Was mixed to obtain a colored curable resin composition.

The coloring pattern was produced by operation similar to Example 1, and the film thickness measurement and chromaticity evaluation were performed.

The results are shown in Table 12.

Comparative Example 1

Colorant: C.I. Pigment green 7 (pigment) 7.5 parts

Colorant: C.I. Pigment yellow 138 (pigment) 7.5 parts

Pigment Dispersant Part 6

Solvent: Propylene glycol monomethyl ether acetate 25 parts

Solvent: 11 parts of ethyl 3-ethoxypropionate

Mixed and dispersed pigment dispersion,

Resin: A copolymer of benzyl methacrylate / methacrylic acid = 70/30 (molar ratio) (acid value is 113; polystyrene equivalent weight average molecular weight is 30,000) 28 parts

Polymerizable compound: dipentaerythritol hexaacrylate 8 parts

Polymerization initiator: 2 parts of IRGACURE 907 (manufactured by BASF)

Surfactant: Megapark F477 (manufactured by DIC Corporation) 2 parts

Solvent: Propylene glycol monomethyl ether acetate 126 parts

Solvent: 54 parts of ethyl 3-ethoxypropionate

Was mixed to obtain a colored curable resin composition.

[Production and Evaluation of Colored Coating Film]

After apply | coating the said colored curable resin composition on the 5 cm square glass substrate (Eagle XG; Corning company make) by the spin coat method, it prebaked at 100 degreeC for 3 minutes. After cooling, light was irradiated with an exposure amount (365 nm standard) of 150 mJ / cm 2 under an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). After light irradiation, it post-baked for 20 minutes in 220 degreeC in oven, and obtained the coloring coating film.

About the obtained colored coating film, it carried out similarly to Example 1, and measured the film thickness and chromaticity evaluation.

The results are shown in Table 12.

From the above result, it was confirmed that the coloring pattern formed from the colored curable resin composition of this invention is excellent in brightness. From this, it turns out that it is possible to manufacture the display apparatus excellent in color performance by making the coloring pattern formed from the colored curable resin composition of this invention into a color filter.

According to the colored curable resin composition of this invention, a high brightness blueish green color filter can be manufactured.

Claims (8)

As colored curable resin composition containing a coloring agent, resin, a polymeric compound, and a polymerization initiator,
The colorant contains a copper chloride phthalocyanine pigment and a yellow dye,
Colored curable resin composition whose content of a yellow dye is 1 mass% or more and 65 mass% or less with respect to the total amount of a coloring agent. The coloring curable resin composition of Claim 1 which is a pigment containing the compound represented by a chlorinated phthalocyanine pigment with a formula (P1).

[In formula (P1), a1, a2, a3 and a4 represent the integer of 0-4 independently of each other, and (a1 + a2 + a3 + a4) is 10 or more and 16 or less.] The chlorinated phthalocyanine pigment according to claim 1, wherein the chlorinated phthalocyanine pigment is C.I. Colored curable resin composition which is pigment green 7. The colored curable resin composition according to any one of claims 1 to 3, wherein the yellow dye is a yellow azo dye. The colored curable resin composition according to claim 4, wherein the yellow azo dye is a dye containing a compound represented by formula (1).

[In Formula (1), A <^0> represents the C6-C14 bivalent aromatic hydrocarbon group which may have a substituent.
B <^0> represents the C6-C14 monovalent heterocyclic group which may have a substituent, and may have a C6-C14 monovalent aromatic hydrocarbon group or substituent.
R <^51> represents the C1-C18 acyl group which may have a hydrogen atom and a substituent, and may have a C1-C16 monovalent saturated hydrocarbon group or a substituent.
p1 represents 1 or 2. When p1 is 2, some A <^0> , B <^0> , R <^51> and R <^52> may mutually be same or different.
If p1 is 1, R ⁵² is, although a hydrogen atom or a substituent group represents a good monovalent saturated hydrocarbon group having 1 to 16 carbons, when p1 is 2, R ⁵² is even have a substituent divalent group having a carbon number of 1 to 35 The saturated hydrocarbon group may be represented and -CH ₂ -contained in the monovalent saturated hydrocarbon group and the divalent saturated hydrocarbon group may be substituted with -O-, -S-, -CO-, or -NR'-.
R 'represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.] The colored curable resin composition of Claim 4 whose yellow azo dye is a compound represented by Formula (2).

Equation (2), Z ^1, Z ² and Z ³ is -CH ₂ respectively to even have a substituent independently represents a good divalent aliphatic hydrocarbon group having a carbon number of 1 to 16, contained in Z ^1, Z ² and Z ³ -May be substituted with -CO- or -O-. R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or a C1-C16 monovalent saturated aliphatic hydrocarbon group which may have a substituent or a C2-C18 acyl group which may have a substituent. A ¹ and A ² each independently represent a C6-C14 divalent aromatic hydrocarbon group which may have a substituent. B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent.] The color filter formed with the colored curable resin composition in any one of Claims 1-6. A display device comprising the color filter according to claim 7.