TWI832828B - Blue curable resin composition, blue color filter and display device containing the same - Google Patents

Abstract

The present invention provides a blue curable resin composition with relatively low x in the xy chromaticity diagram in the XYZ color system and high brightness, a blue color filter formed from the blue curable resin composition, and A display device containing the blue color filter. A blue curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the colorant (A) contains C.I. Pigment Blue 15 , with red dye or purple dye.

Description

Blue curable resin composition, blue color filter and display device containing the same

The present invention relates to a blue curable resin composition, a blue color filter and a display device containing the same.

In recent years, there has been an increase in demand for liquid crystal display devices capable of displaying a wide color reproduction range.

Patent Document 1 proposes a composition including a combination of C.I. pigment blue (pigment blue) 15 and C.I. pigment violet (pigment violet) 23. Patent Document 2 proposes a composition containing C.I. Pigment Blue 15:6 and a red dye.

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2005-316388

[Patent Document 2] Japanese Patent Application Publication No. 2010-32999

In order to obtain a display device with a wide displayable color reproduction range, an object of the present invention is to provide a blue curable resin composition with low x in the xy chromaticity diagram in the XYZ color system and high brightness. Blue color formed from a plastic resin composition Optical filter, and a display device containing the blue color filter.

The present invention provides a blue curable resin composition, a blue color filter, and a display device shown below.

[1] A blue curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) contains C.I. Pigment blue 15, with red dye or purple dye.

[2] The blue curable resin composition according to [1], wherein the red dye or purple dye contained in the colorant (A) is a compound having a xanthene skeleton.

[3] The blue curable resin composition according to [2], wherein the content of the compound having a xanthene skeleton in the colorant (A) is 0.1% by mass to 25% by mass.

[4] A blue color filter formed from the blue curable resin composition according to any one of [1] to [3].

[5] A display device including the blue color filter according to [4].

According to the blue curable resin composition of the present invention, it is possible to provide a blue color filter with low x in the xy chromaticity diagram in the XYZ color system and high brightness, and a display device containing the same.

<Blue curable resin composition>

The blue curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) contains C.I. Pigment Blue 15, and Red dye or purple dye.

The blue curable resin composition containing C.I. Pigment Blue 15 in a specific combination with a red dye or a violet dye can reduce the x of the xy chromaticity diagram in the XYZ color system and increase the brightness.

The so-called x of the xy chromaticity diagram in the XYZ color system (hereinafter also referred to as The x coordinate (x) of blue (B) in the xy chromaticity coordinates (x, y).

When y (hereinafter also referred to as y) in the xy chromaticity diagram in the wide tendency.

Brightness refers to the stimulation value Y in the XYZ color system, and the larger the Y value, the higher the brightness.

The chromaticity coordinates and brightness of the xy chromaticity diagram in the XYZ colorimetric system were measured in accordance with "(4) Chromaticity evaluation" described in the Example column described later.

In addition, in this specification, the compound exemplified as each component can be used individually or in combination of multiple types unless otherwise specified.

[1] Colorant (A)

In the blue curable resin composition of the present invention, the colorant (A) contains C.I. Pigment blue 15, with red dye or purple dye. Since the blue curable resin composition contains the colorant (A), it can lower the x of the xy chromaticity diagram in the XYZ color system and improve the brightness, so it is useful as a material for a blue color filter.

C.I. Pigment Blue 15 is a compound classified as a blue pigment in the Color Index (C.I.: Color Index, published by The Society of Dyers and Colourists).

The so-called blue curable resin composition refers to one that has a maximum absorption wavelength between 580nm and 650nm.

Any one of the red dye and the purple dye may be included in the colorant (A), or both of them may be included in the colorant (A). Therefore, the blue curable resin composition includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) may include C.I. Pigment Blue 15 , with red dye and/or purple dye.

The red dye refers to a dye with a maximum absorption wavelength in 480nm~560nm, and the purple dye refers to a dye with a maximum absorption wavelength in 560nm~580nm.

As the red dye and the purple dye, one or more of conventionally known red dyes and purple dyes can be used, respectively. From the viewpoint that there is a tendency to increase brightness, the red dye and the purple dye are each preferably a compound having a xanthene skeleton (hereinafter also referred to as a “xanthene dye”).

The xanthene dye is preferably a compound represented by the following formula (1) [hereinafter, also referred to as "xanthene dye (1)"]. Only one type of xanthene dye (1) can be used alone, Two or more types may be used together.

[In formula (1), R ¹ to R ⁴ independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms, or R ¹ and R ² and R ³ and R ⁴ are formed together respectively. A ring containing nitrogen atoms; the hydrogen atoms contained in the aromatic hydrocarbon group can be passed through halogen atoms, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , - CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ substitution; as the halogen atom, it can be enumerated: fluorine atom, chlorine atom, bromine atom, iodine atom; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H , -SO ₃ ^- M ⁺ , -CO ₂ H , -CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ ;m represents an integer from 0 to 5; when m is an integer of 2 or more, multiple R ⁵ may be the same or different from each other; R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms. ; M ⁺ represents ⁺ N(R ¹¹ ) ₄ ^, Na ⁺ or K ⁺ ; Represents a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group with 6 to 10 carbon atoms or a halogen atom. The -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -S-, -O-, -CO- or -NR ¹¹ -substitution; R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms or an aralkyl group with 7 to 10 carbon atoms; there are ^multiple In the case of two, all or part of these may be the same; R ⁹ and R ¹⁰ independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be - OH or halogen atom substituted, -CH ₂ - contained in the saturated aliphatic hydrocarbon group can be substituted by -S-, -O-, -CO-, -NH- or -NR ⁸ -; R ⁹ and R ¹⁰ can be substituted with each other Bonded to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom; examples of halogen atoms include: fluorine atom, chlorine atom, bromine atom, and iodine atom]

Among R ¹ to R ⁴ in the formula (1), examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl, toluylyl, xylyl, mesityl, and propylbenzene. base and butylphenyl, etc.

Among R ¹ to R ⁴ in formula (1), the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably one selected from the group consisting of -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ and -SO ₂ As ^a substituent, at least one type selected from the group consisting of _{-SO 3} ^{- M +} and -SO ₂ NR ⁹ R ¹⁰ is more preferred. -SO ₃ ^- M ⁺ in this case is preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ . When R ¹ to R ⁴ are these groups, it is advantageous in terms of forming a blue color filter excellent in heat resistance.

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include the following rings. In the following rings, * indicates a bonding bond.

Among R ⁸ to R ¹¹ in the formula (1), examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and pentyl. , isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl and other carbon numbers 1 to 20 Alkyl; cycloalkyl groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, etc.

Regarding the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ , examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in which a hydrogen atom may be substituted include: phenyl group, toluylyl group, xylyl group, and mesitylene group. Tolyl, propylphenyl and butylphenyl, etc. Examples of the group in which -CH ₂ - contained in R ⁸ is substituted with -S-, -O-, -CO- or -NR ¹¹ - include the following groups. In the following bases, * represents a bond.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ in formula (1) include those having 1 to 6 carbon atoms among the alkyl groups listed above.

Examples of the group represented by -SO ₂ NR ⁹ R ¹⁰ include groups represented by the following formula. In the following bases, * represents a bond.

CX⁰ ₃(CX⁰)₂CH₂NHSO₂ *

CX ⁰ ₃ (CX ⁰ ) ₂ CH ₂ NHSO ₂ *

In the formula, X ⁰ and X ² independently represent a halogen atom. Examples of the halogen atom in X ⁰ and X ² include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ in formula (1) include benzyl group, phenylethyl group, phenylbutyl group, and the like.

M ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ . ⁺ N(R ¹¹ ) ₄ preferably means that at least two of the four R ¹¹ are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total carbon number of four R ¹¹ is preferably 20 to 80, more preferably 20 to 60.

The xanthene dye (1) is preferably a compound represented by formula (2).

[In the formula (2), R ²¹ to R ²⁴ independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group can be replaced by -SO ₃ ^- , -SO ₃ ^- M ^a+ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ substituted; ;a1 represents 0 or 1.

m1 represents an integer from 0 to 5; when m1 is an integer above 2, multiple R ²⁵ may be the same or different; M ^a+ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ ; R ²⁵ represents -SO ₃ ^- , -SO ₃ ^- Ma ⁺ , -SO ₃ H or SO ₂ NHR ²⁶ ; R ²⁶ represents a monovalent saturated hydrocarbon group with a carbon number of 1 to 20; four R ²⁷ independently represent a carbon number of 1 to 20 Monovalent saturated hydrocarbon group or benzyl group]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ in the formula (2) include the same groups as those exemplified as the aromatic hydrocarbon group in R ¹ to R ⁴ . Among them, it is preferable that R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and when the hydrogen atoms contained in the aromatic hydrocarbon group are substituted , the substituted group is -SO ₃ ^- , -SO ₃ ^- M ⁺ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . Furthermore, it is more preferable that R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups can be replaced by -SO ₃ ^- M ⁺ or -SO ₂ NHR ²⁶ substituted. When R ²¹ to R ²⁴ are these groups, it is advantageous in terms of forming a blue color filter excellent in heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ in the formula (2) include the same groups as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ . -R ²⁶ among R ²¹ to R ²⁴ in formula (2) is preferably each independently a hydrogen atom, a methyl group or an ethyl group.

R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ in formula (2) is preferably a branched chain alkyl group having 3 to 20 carbon atoms, and more preferably is a branched chain alkyl group having 6 to 12 carbon atoms. Alkyl group, more preferably 2-ethylhexyl group.

M ^a+ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ . ⁺ N(R ²⁷ ) ₄ preferably has at least two of the four R ^27s being monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total carbon number of four R ²⁷ is preferably 20 to 80, more preferably 20 to 60.

The xanthene dye (1) preferably contains at least one compound represented by formula (1-1) to formula (1-16). In addition, in formula (1-1) to formula (1-16), Ra represents 2-ethylhexyl.

Among these compounds, the sulfonamide compound of C.I. acid red 289 or the quaternary ammonium salt of C.I. acid red 289 is more preferred. Examples of such compounds include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12), respectively.

For example, compounds represented by Formula (1-1) to Formula (1-8) and Formula (1-15) can be produced by chlorinating a pigment or pigment intermediate having -SO ₃ H using a general method. , and react the obtained pigment or pigment intermediate having -SO ₂ Cl with the amine represented by -NH ₂ R _a . In addition, it can also be produced by chlorinating the dye produced by the method described in the upper right column to the lower left column on page 3 of Japanese Patent Application Laid-Open No. 3-78702 in the same manner as described above, and then reacting it with an amine. .

Other preferred xanthene dyes (1) include any one or more of the compounds represented by formulas (1-17) to (1-31).

The compounds represented by Formula (1-17) to Formula (1-31) can be produced according to the method described in the upper right column to the lower left column on page 3 of Japanese Patent Application Laid-Open No. 3-78702. Examples of the method include a method of reacting a compound represented by formula (1a), a compound represented by formula (1b), and a compound represented by formula (1c). In formula (1b) and formula (1c), R ¹ to R ⁴ each have the same meaning as described above.

As the xanthene dye (1), commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Kasei Co., Ltd., "Rhodamine" manufactured by Tagang Chemical Industry Co., Ltd.) can be used Rhodamin)6G"). Alternatively, commercially available xanthene dyes can be used as starting materials and can be synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999.

Specific examples of the xanthene dye (1) include C.I. acid red 51 (hereinafter, description of C.I. acid red will be omitted and only the number will be described. The same applies to others), 52, 87, 92, 94, 289, 388, etc. C.I. acid red dye; C.I. acid violet (acid violet) 9, 30, 102, etc. C.I. acid violet dye; C.I. basic red (basic red) 1 (rhodamine (rhodamine) 6G), 2, 3, 4, 8, 10, 11, etc. C.I. basic red dye; C.I. alkali Basic violet (basic violet) 10 (rhodamine B), 11, 25, etc. C.I. basic violet dye; C.I. solvent red (solvent red) 218, etc. C.I. solvent red dye; C.I. mordant red (mordant red) 27, etc. C.I. mordant red Dyes; C.I. reactive red (reactive red) 36 (rose bengal B) and other C.I. reactive red dyes; sulforhodamine (sulforhodamine) G; oxa described in Japanese Patent Laid-Open No. 2010-32999 Anthracene dyes; and xanthene dyes described in Japanese Patent No. 4492760, etc.

The content ratio of C.I. Pigment Blue 15 in the colorant (A) to the red dye or violet dye, or the total content ratio of the red dye and the violet dye when both are included (C.I. Pigment Blue 15/red dye or violet dye, or a red dye and a purple dye when both are included) is usually 0.8 to 35 on a mass basis, and from the viewpoint that x tends to become lower and the brightness becomes higher, it is preferably 1 to 25, more preferably It is 1.1~20, preferably 1.2~15.

The colorant (A) may include colorants other than C.I. Pigment Blue 15, red dye, and/or violet dye. The other colorant may be a pigment (hereinafter, also referred to as other pigment), a dye (hereinafter, also referred to as other dye), or both of these. Only one type of other colorants may be used, or two or more types may be used in combination. Examples of other pigments include organic pigments and inorganic pigments, and compounds classified as pigments in the Dye Index (published by The Society of Dyers and Colourists).

As other dyes, well-known dyes can be used, and examples include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Examples of dyes include compounds having hues other than pigments classified in the Dye Index (published by The Society of Dyers and Colourists), or Dyeing Notes (Shikisensha Co., Ltd.) Well-known dyes described in . In addition, based on the chemical structure, examples include azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and azomethine dyes. Dyes, squarylium dyes, acridine dyes, styrene-based dyes, coumarin dyes, quinoline dyes, nitro dyes, etc. Among these, organic solvent-soluble dyes are preferred.

The colorant (A) may include other blue colorants (blue pigments and/or blue dyes) other than C.I. Pigment Blue 15. Examples of other blue pigments include C.I. Pigment Blue 15:3, 15:4, 15:6, 16, 60, and the like.

Examples of blue dyes include: C.I. solvent blue (solvent blue) 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78 , 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, etc. C.I. solvent blue dye; C.I. acid blue (acid blue) 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340, etc. C.I. acid blue dye; C.I. direct blue (direct blue) 1, 2, 3, 6, 8, 15 ,22,25,28,29,40,41,42,47,52,55,57,71,76,77,78,80,81,84,85,86,90,93,94,95,97 ,98,99,100,101,106,107,108,109,113,114,115,117,119,120,137,149,150,153,155,156,158,159,160,161,162 ,163,164,165,166,167,168,170,171,172,173,188,189,190,192,193,194,195,196,198,199,200,201,202,203,207 ,209,210,212,213,214,222,225,226,228,229,236,237,238,242,243,244,245,246,247,248,249,250,251,252,256 , 257, 259, 260, 268, 274, 275, 293, etc. C.I. direct blue dye; C.I. disperse blue (disperse blue) 1, 14, 56, 60, etc. C.I. disperse blue dye; C.I. basic blue (basic blue) 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89, etc. C.I. basic blue dye; C.I. mordant blue (mordant blue) 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, etc. C.I. media Blue dye; etc.

Among them, from the viewpoint of lowering x and improving brightness, the total of C.I. Pigment Blue 15 in the colorant (A), the red dye or the purple dye, or the red dye and the purple dye when both are included The higher the content, the better. Specifically, the total content of C.I. Pigment Blue 15, the red dye or the purple dye, or the red dye and the purple dye when both of them are included in the colorant (A) is 100% by mass of the colorant (A) Among them, 50 mass% to 100 mass% is preferred, 70 mass% to 100 mass% is more preferred, 80 mass% to 100 mass% is further preferred, and 90 mass% to 100 mass% is particularly preferred.

The content of C.I. Pigment Blue 15 in the colorant (A) is usually 20 mass% to 99.9 mass% in 100 mass% of the colorant (A). From the viewpoint that x tends to be low, 40 is preferred. Mass % to 95 mass %, more preferably 50 mass % to 90 mass %.

The content of the red dye or purple dye in the colorant (A), or the red dye and the purple dye when both are included, is usually 0.1% by mass to 80% by mass in 100% by mass of the colorant (A). From the viewpoint that the brightness tends to increase, the content is preferably 5% to 60% by mass, and more preferably 10% to 40% by mass.

When the colorant (A) contains a xanthene dye as a red dye and a purple dye, the content of the xanthene dye in the colorant (A) is preferably 0.1 mass% in 100% by mass of the colorant (A) %~25 mass%, preferably 0.5 mass%~20 mass%, preferably 1 mass% to 15 mass%. When the colorant (A) contains a xanthene dye in the content within the above range, the brightness tends to become high.

The total content of the colorant (A) in the blue curable resin composition is usually 10% to 50% by mass based on 100% by mass of the solid content of the blue curable resin composition. There is an XYZ color system. From the viewpoint of the tendency for x in the xy chromaticity diagram to become lower and the brightness to become higher, 15 mass % or more is preferred, 20 mass % to 40 mass % is more preferred, and 25 mass % to 35 mass % is more preferred. From the viewpoint of easy formation of a resist pattern, the total content is preferably 45 mass% or less in 100 mass% of the solid content of the blue curable resin composition.

According to the present invention, by setting the total content of the colorant (A) to an appropriate amount, deterioration of the pattern shape and the like can be suppressed, and a blue color filter with low x and high brightness can be formed.

In addition, in this specification, "the solid content of the blue curable resin composition" means all components except the solvent (E) among the components contained in the blue curable resin composition.

It is preferable that the various pigments used for the preparation of the blue curable resin composition are in the state of a dispersion liquid uniformly dispersed in a solvent. In addition, the pigment preferably has a uniform particle size. The dispersion can be obtained by mixing the pigment with a solvent. Pigment dispersants can also be mixed if necessary. By containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in a state in which the pigment is uniformly dispersed in the solvent can be obtained.

As the pigment dispersant, commercially available surfactants can be used, including silicone-based, fluorine-based, ester-based (including polyester-based), cationic, anionic, nonionic, and amphoteric surfactants. Polyester, polyamine, acrylic and other surfactants. Specific examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid-modified polyesters. In addition to tertiary amine-modified polyurethanes, polyethylenimines, etc., trade names include KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Flowlen (Kyoeisha Chemical Co., Ltd.) Manufactured), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Ajisper (registered Trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), etc. Only one type of pigment dispersant may be used, or two or more types of pigment dispersants may be used in combination.

When a pigment dispersant is used, the usage amount is preferably 100 parts by mass or less, and more preferably 5 to 50 parts by mass based on 100 parts by mass of the pigment. When the usage amount of the pigment dispersant is within the above range, a pigment dispersion liquid in a uniform dispersed state tends to be easily obtained.

The solvent constituting the pigment dispersion is not particularly limited, and examples thereof include the same solvent (E) described below that may be contained in the blue curable resin composition. Among them, preferred solvents are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, 3-methoxybutylacetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide Amines, etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl Acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, etc.

The usage amount of the solvent is not particularly limited, but is an amount such that the concentration of the solid content in the pigment dispersion becomes preferably 5% to 30% by mass, more preferably 10% to 25% by mass.

Various pigments used in the preparation of the blue curable resin composition may be subjected to rosin treatment, surface treatment using pigment derivatives or pigment dispersants introducing acidic groups or basic groups, or use of polymer compounds as necessary. Grafting treatment on the surface of the pigment, micronization treatment using sulfuric acid micronization method, etc., or cleaning treatment using organic solvents or water to remove impurities, removal treatment of ionic impurities using ion exchange method, etc. wait.

[2] Resin (B)

The blue curable resin composition of the present invention contains one or more resins (B). Resin (B) is preferably an alkali-soluble resin. Alkali solubility refers to the property of dissolving in an aqueous solution of an alkali compound, that is, a developer. Examples of the resin (B) include the following resin [K1] to resin [K6].

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

Resin [K2]: (a) and (b) and the monomer (c) copolymerizable with (a) (which is different from (a) and (b)) [hereinafter, sometimes referred to as "(c) "] copolymer.

Resin [K3]: Copolymer of (a) and (c).

Resin [K4]: Resin obtained by reacting the copolymer of (b) and (a) with (c).

Resin [K5]: Resin obtained by reacting the copolymer of (a), (b) and (c).

Resin [K6]: A resin obtained by reacting a copolymer of (a), (b) and (c), and further reacting a carboxylic acid anhydride.

Specific examples of (a) include: (meth)acrylic acid, crotonic acid, unsaturated monocarboxylic acids such as o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; maleic acid , fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid Formic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid and other unsaturated dicarboxylic acids; methyl-5-dicarboxylic acid Bornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5- Methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept- 2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl Phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl tetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (5-norbornene-2,3-dicarboxylic anhydride (himic anhydride)) and other unsaturated dicyclic Carboxylic acid anhydrides; succinic acid mono[2-(meth)acryloxyethyl] ester, phthalic acid mono Unsaturated mono[(meth)acryloxyalkyl] esters of divalent or higher polycarboxylic acids such as [2-(meth)acryloxyethyl] ester; such as α-(hydroxymethyl) ) Unsaturated (meth)acrylic acid containing hydroxyl and carboxyl groups in the same molecule like (meth)acrylic acid.

Among them, (a) is preferably (meth)acrylic acid, maleic anhydride, etc. from the viewpoint of copolymerization reactivity or solubility in an alkaline aqueous solution.

In addition, in this specification, "(meth)acrylic acid group" means at least one selected from the group consisting of an acrylic acid group and a methacrylic acid group. The same applies to the expressions such as "(meth)acrylyl" and "(meth)acrylate".

(b) refers to a cyclic ether structure having 2 to 4 carbon atoms (for example, selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring) at least one) polymerizable compound with an ethylenically unsaturated bond. (b) Preferably, it is a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloxy group.

Examples of (b) include monomers (b1) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as “(b1)”], monomers having an oxetanyl group and an ethylenically unsaturated bond. The monomer (b2) of an unsaturated bond [hereinafter, sometimes referred to as "(b2)"], and the monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "(b3)" )"〕wait.

Examples of (b1) include monomers (b1-1) having a structure obtained by epoxidizing unsaturated aliphatic hydrocarbons (hereinafter, sometimes referred to as “(b1-1)”), and monomers having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon A monomer (b1-2) of a structure obtained by epoxidation of a cyclic hydrocarbon [hereinafter sometimes referred to as is "(b1-2)"].

Examples of (b1-1) include (glycidylmeth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidylvinyl Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-methylene Benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl) styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyl)styrene Oxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4, 5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

Examples of (b1-2) include: vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Daicel) Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer A400; Daicel Chemical Industry Co., Ltd.), (meth) 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.), compounds represented by formula (I), compounds represented by formula (II) Compounds etc.

[In formula (I) and formula (II), R ^aa and R ^ab independently represent a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X ^a1 and X ^a2 independently represent a single bond, *-R ^ac - ^, *-R ^ac -O-, *-R ^ac -S-, or *-R ^ac -NH-; Alkanediyl; * indicates the bond with O]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, and the like.

Examples of alkyl groups in which hydrogen atoms are substituted with hydroxyl groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1 -Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

R ^aa and R ^ab are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkylenediyl group constituting R ^ac include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane. -1,5-diyl, hexane-1,6-diyl, etc.

_X ^{a1 and} _{_ _} Preferably it is a single bond, *-CH ₂ CH ₂ -O- group.

Specific examples of the compound represented by formula (I) include compounds represented by formula (I-1) to formula (I-15), and preferably, compounds represented by formula (I-1) and formula (I-3) ), compounds represented by formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), more preferably, compounds represented by formula (I- 1), compounds represented by formula (I-7), formula (I-9), and formula (I-15).

Specific examples of the compound represented by formula (II) include compounds represented by formula (II-1) to formula (II-15), and preferably, compounds represented by formula (II-1) and formula (II-3) ), compounds represented by formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), more preferably, compounds represented by formula (II- 1), compounds represented by formula (II-7), formula (II-9), and formula (II-15).

The compound represented by formula (I) and the compound represented by formula (II) can be used individually. These can be mixed in any ratio. In the case of mixing, the mixing ratio is calculated as formula (I): formula (II) [molar ratio], preferably 5:95~95:5, more preferably 10:90~90:10, and further The best time is 20:80~80:20.

The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloxy group.

Preferable examples of (b2) include: 3-methyl-3-(meth)acryloxymethyloxetane, 3-ethyl-3-(meth)acrylyl Oxymethyloxetane, 3-methyl-3-(meth)acryloxyethyloxetane, 3-ethyl-3-(meth)acryloxy Ethyloxetane.

The monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuran group and a (meth)acryloxy group. Preferable examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

Specific examples of (c) include: (methyl)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second-butyl (meth)acrylate, (meth)acrylate tert-butyl acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth) Cyclopentyl acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate[ In this technical field, it is called "dicyclopentyl (meth)acrylate" as a common name. In addition, it may also be called "(meth)acrylic acid tricyclodecyl ester", (meth)acrylic acid tricyclo[5.2.1.0 ^2,6 ] decene-8-yl ester [in this technical field, it is commonly used as Named "dicyclopentenyl (meth)acrylate"], dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantane (meth)acrylate (meth)acrylic acid, such as allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, etc. Esters; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; diethyl maleate, diethyl fumarate ester, diethyl itaconate and other dicarboxylic acid diesters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2 .1]Hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl ) Bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6 -Dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl) Bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene En, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5- Methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2 -ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6- Bicyclic unsaturated compounds such as bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N -Benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide Butyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimide propionate, N-(9 Dicarbonyl imide derivatives such as -acridinyl)maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy Styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3 -Dimethyl-1,3-butadiene, etc.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, (c) is preferably benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, or N-phenylmaleyl Imine, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. In addition, in terms of excellent developability during pattern formation, (c) is more preferably benzyl (meth)acrylate or tricyclodecyl (meth)acrylate.

Among all the structural units constituting the resin [K1], the ratio of the structural units derived from each in the resin [K1] is preferably in the following range.

Structural units derived from (a): 2 mol% to 50 mol% (more preferably 10 mol% to 45 mol%); structural units derived from (b), especially those derived from (b1) Structural unit: 50 mol% ~ 98 mol% (more preferably 55 mol% ~ 90 mol%).

When the ratio of the structural units of the resin [K1] is within the above range, storage stability, developability, and solvent resistance of the obtained pattern tend to be excellent.

For resin [K1], please refer to the method described in the document "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, Chemical Doujin Publishing Co., Ltd., 1st edition, 1st printing, issued on March 1, 1972) and the method described therein Manufactured based on citations recorded in the literature.

Specific examples include a method in which predetermined amounts of (a) and (b) (especially (b1)), a polymerization initiator, a solvent, etc. are put into a reaction vessel, and stirred, heated, and kept warm in a deoxygenated environment. . In addition, the polymerization initiator, solvent, etc. used here are not particularly limited, and those commonly used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (Benzyl peroxide, etc.). The solvent may be any one that dissolves each monomer, and a solvent (E) described below as a solvent for the blue curable resin composition, etc. can be used.

The obtained copolymer can be used directly as a reacted solution, as a concentrated or diluted solution, or as a solid (powder) extracted by a method such as reprecipitation. In particular, during this polymerization, by using a solvent (E) described below as a solvent, The reacted solution can be used directly, thus simplifying the manufacturing steps.

Among all the structural units constituting the resin [K2], the ratio of the structural units derived from each in the resin [K2] is preferably in the following range.

Structural units derived from (a): 4 mol% to 45 mol% (more preferably 10 mol% to 30 mol%); structural units derived from (b), especially those derived from (b1) Structural unit: 2 mol% to 95 mol% (more preferably 5 mol% to 80 mol%); structural unit derived from (c): 1 mol% to 65 mol% (more preferably 5 Mol%~60mol%).

When the ratio of the structural units of the resin [K2] is within the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength of the obtained pattern tend to be excellent.

The resin [K2] can be produced in the same manner as the method described as the production method of the resin [K1]. Specifically, predetermined amounts of (a), (b) (especially (b1)), and (c), a polymerization initiator, and a solvent are put into a reaction vessel, and stirred and heated in a deoxygenated environment. Methods of insulation. The obtained copolymer can be used directly as a reacted solution, as a concentrated or diluted solution, or as a solid (powder) extracted by a method such as reprecipitation.

Among all the structural units constituting the resin [K3], the ratio of the structural units derived from each in the resin [K3] is preferably in the following range.

Structural unit derived from (a): 2 mol% to 55 mol% (more preferably 10 mol% to 50 mol%); Structural unit derived from (c): 45 mol% to 98 mol% (more preferably 50 mol% to 90 mol%).

The resin [K3] can be produced in the same manner as the method described as the production method of the resin [K1].

Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and converting the cyclic ether structure having 2 to 4 carbon atoms in (b), especially the oxyheterocyclic ring having (b1) Propane is cycloadded to the carboxylic acid and/or carboxylic acid anhydride contained in (a). Specifically, first, the copolymer of (a) and (c) is produced in the same manner as described as the method for producing resin [K1]. In this case, among all the structural units constituting the copolymer of (a) and (c), the ratio of the structural units derived from each is preferably in the following range.

Structural unit derived from (a): 5 mol% to 50 mol% (more preferably 10 mol% to 45 mol%); structural unit derived from (c): 50 mol% to 95 mol% % (more preferably 55 mol%~90 mol%).

Next, the cyclic ether structure having 2 to 4 carbon atoms in (b), particularly the oxirane ring in (b1), and the carboxylic acid and/or carboxylic acid derived from (a) in the copolymer are A portion of the anhydride reacts. Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) (especially (b1)), carboxylic acid or carboxylic acid anhydride and cyclic ether are Add structural reaction catalysts (such as tris(dimethylaminomethyl)phenol, etc.) and polymerization inhibitors (such as hydroquinone, etc.) into the flask, and react at 60°C to 130°C for 1 hour to 10 hours. , whereby resin [K4] can be obtained.

The usage amount of (b), especially (b1), is preferably from 5 moles to 80 moles, more preferably from 10 moles to 75 moles, relative to 100 moles of (a). By setting it as this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to become good. Since the cyclic ether structure has high reactivity and unreacted (b) hardly remains, the (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1) .

The usage amount of the reaction catalyst is preferably 0.001 mass% to 5 mass% relative to the total amount of (a), (b) (especially (b1)) and (c). The usage amount of the polymerization inhibitor is preferably 0.001 mass% to 5 mass% relative to the total amount of (a), (b) and (c).

Reaction conditions such as the input method, reaction temperature and time can be appropriately adjusted taking into consideration the production equipment or the calorific value of polymerization. In addition, similarly to the polymerization conditions, the input method and the reaction temperature can be appropriately adjusted by taking into consideration the production equipment, the calorific value of polymerization, and the like.

Regarding the resin [K5], as a first step, a copolymer of (b) (especially (b1)) and (c) is obtained in the same manner as in the production method of the resin [K1]. In the same manner as described above, the obtained copolymer can be used directly as a reacted solution, a concentrated or diluted solution, or a copolymer extracted as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) (especially (b1)) and (c) relative to the total molar number of all structural units constituting the copolymer is preferably in the following range.

Structural units derived from (b), in particular from (b1): 5 mo Mol%~95 Mol% (more preferably 10 Mol%~90 Mol%); Structural unit derived from (c): 5 Mol%~95 Mol% (more preferably 10 Mol%~90 mol%).

Furthermore, under the same conditions as the production method of resin [K4], the carboxylic acid or carboxylic acid anhydride contained in (a) and the copolymer derived from (b) (especially (b1)) and (c) are produced ), the resin [K5] can be obtained by reacting with the cyclic ether structure. The usage amount of (a) reacted with the copolymer is preferably 5 moles to 80 moles relative to 100 moles of (b) (especially (b1)). Since the cyclic ether structure has high reactivity and unreacted (b) hardly remains, the (b) used in the resin [K5] is preferably (b1), and more preferably (b1-1) .

Resin [K6] is a resin obtained by further reacting carboxylic acid anhydride and resin [K5]. Carboxylic anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether structure with carboxylic acid or carboxylic anhydride.

Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrakis Hydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2- Alkene anhydride (5-norbornene-2,3-dicarboxylic anhydride), etc.

Among resin [K1] to resin [K6], a preferred resin as the resin (B) is [K1] or [K2]. Resin (B) may contain one type of resin or two or more types of resin.

The weight average molecular weight (Mw) in terms of polystyrene of resin (B) is relatively The preferred range is 3,000~100,000, the more preferred range is 5,000~50,000, the further preferred range is 5,000~30,000, the further preferred range is 8,000~15,000. When the weight average molecular weight (Mw) is within the above range, the solubility of the unexposed portion to the developer is high, and the resulting pattern tends to have a high residual film rate or hardness. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value of the resin (B) in terms of solid content is preferably 5 mg-KOH/g to 200 mg-KOH/g, more preferably 50 mg-KOH/g to 180 mg-KOH/g, and even more preferably 80 mg-KOH/g. g~150mg-KOH/g, and more preferably 90mg-KOH/g~130mg-KOH/g. The acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin, and can be determined by titration using a potassium hydroxide aqueous solution, for example.

The content of the resin (B) is preferably 5% to 50% by mass, more preferably 10% to 45% by mass, and even more preferably 15% by mass in 100% by mass of the solid content of the blue curable resin composition. ~40% by mass. When the content of the resin (B) is within the above range, the solubility of the unexposed portion to the developer tends to be high.

[3]Polymerizable compound (C)

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) due to light irradiation, etc. Examples of the polymerizable compound (C) include polymerizable ethylenically unsaturated compounds. Bonded compounds, etc. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.

Among these, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and examples thereof include: trimethylolpropane tris(methyl) Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate , tripentaerythritol hepta(meth)acrylate, pentaerythritol deca(meth)acrylate, pentaerythritol nona(meth)acrylate, tris(2-(meth)acryloxyethyl)isocyanurea Acid ester, 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 (meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferred.

The blue curable resin composition of the present invention may contain one or more polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, more preferably 50 to 120 parts by mass relative to 100 parts by mass of the resin (B) in the blue curable resin composition.

[4]Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include oxime-based compounds such as O-acyl oxime compounds, phenylalkyl ketone compounds, biimidazole compounds, triazine compounds, acyl phosphine oxide compounds, and the like.

The polymerization initiator (D) takes into consideration the sensitivity, the formation of precise pattern shapes, etc. Two or more types may be used together. It is preferable that the polymerization initiator (D) contains an oxime-based compound such as an O-hydroxyoxime compound, in view of advantages in terms of sensitivity and precise correction of a pattern shape having a desired line width.

The O-acyl oxime compound is a compound having a structure represented by formula (d). In the following, * indicates a bonding key.

The O-acyl oxime compound is preferably selected from the compound represented by formula (d1) (hereinafter, sometimes referred to as "compound (d1)") and the compound represented by formula (d2) (hereinafter, sometimes referred to as "compound (d1)") At least one of the group consisting of compound (d2)") and a compound represented by formula (d3) (hereinafter, sometimes referred to as "compound (d3)").

[In formulas (d1) to formula (d3), R ^d1 represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have a substituent, a heterocyclic group with 3 to 36 carbon atoms that may have a substituent, or a heterocyclic group with 3 to 36 carbon atoms that may have a substituent. An alkyl group having 1 to 15 carbon atoms, or an optionally substituted group formed by combining an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group, and the methylene group (-CH ₂ contained in the alkyl group -) can be substituted with -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 -; R ^d2 represents an aromatic hydrocarbon group with 6 to 18 carbon atoms or a heterocyclic group with 3 to 36 carbon atoms Or an alkyl group with 1 to 10 carbon atoms; R ^d3 represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have a substituent or a heterocyclic group with 3 to 36 carbon atoms that may have a substituent; R ^d4 represents an optional substituent. An aromatic hydrocarbon group with 6 to 18 carbon atoms or an aliphatic hydrocarbon group with 1 to 15 carbon atoms that may have a substituent, and the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group may be substituted with -O -, -CO- or -S-, the methine group (-CH<) contained in the aliphatic hydrocarbon group may be substituted with -PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with OH Substituted with a base; R ^d5 represents an alkyl group with 1 to 10 carbon atoms, and the methylene group (-CH ₂ -) contained in the alkyl group can be substituted with -O- or -CO-]

The carbon number of the aromatic hydrocarbon group represented by R ^d1 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, and the like. Preferably, phenyl and naphthyl are included, and more preferably, phenyl is included.

The aromatic hydrocarbon group represented by R ^d1 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, and more preferably is substituted at the γ-position.

Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl Alkyl groups with 1 to 15 carbon atoms such as tetradecyl and pentadecyl groups; halogen atoms such as fluorine atoms, chlorine atoms, iodine atoms, bromine atoms, etc.

The carbon number of the alkyl group as the substituent is preferably 1 to 10, more preferably 1 to 7. The alkyl group as this substituent may be any of a linear group, a branched chain group, and a cyclic group, or may be a combination of a chain group and a cyclic group. The methylene group (-CH ₂ -) contained in the alkyl group as the substituent may be substituted with -O- or -S-. In addition, the hydrogen atom contained in the alkyl group may be substituted by a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom, and is preferably substituted by a fluorine atom.

In the aromatic hydrocarbon group represented by R ^d1 , examples of the alkyl group as a substituent include groups represented by the following formula, and the like. In the formula, * represents the bonding bond.

Examples of the optionally substituted aromatic hydrocarbon group represented by R ^d1 include groups represented by the following formulas, and the like. In the formula, * represents the bonding bond.

In R ^d1 , the aromatic hydrocarbon group which may have a substituent is preferably a group represented by the following formula.

[In the formula, R ^d6 represents an alkyl group with 1 to 10 carbon atoms that can be substituted by a halogen atom, and the hydrogen atom contained in R ^d6 can be substituted with a halogen atom; m2 represents an integer from 1 to 5; * represents a bond ]

Examples of the alkyl group represented by R ^d6 include the same alkyl groups exemplified as the substituents of the aromatic hydrocarbon group represented by R ^d1 . The carbon number of R ^d6 is preferably 2 to 7, more preferably 2 to 5. In addition, the alkyl group represented by R ^d6 may be linear, branched, or cyclic, and is preferably chain.

Examples of the halogen atom that can substitute the hydrogen atom contained in R ^d6 include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and a fluorine atom is particularly preferred. It is preferable that 2 or more and 10 or less hydrogen atoms contained in R ^d6 are substituted by halogen atoms, and more preferably 3 or more and 6 or less hydrogen atoms are substituted by halogen atoms. The substitution position of R ^d6 O- group is preferably ortho position or para position, particularly preferably para position. The preferred range of m2 is 1~2, and the particularly preferred range is 1.

The number of carbon atoms in the heterocyclic group represented by R ^d1 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, and the like.

The heterocyclic group represented by R ^d1 may have one or more substituents. Examples of the substituent include the same groups as those exemplified as the substituents that the aromatic hydrocarbon group represented by R ^d1 may have.

The carbon number of the alkyl group represented by R ^d1 is preferably 1 to 12. Examples of the alkyl group represented by R ^d1 include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl , tridecyl, tetradecyl and pentadecyl, etc. These alkyl groups may be linear, branched, or cyclic, or may be a combination of a chain group and a cyclic group. In addition, in the alkyl group represented by R ^d1 , the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 -, and a hydrogen atom may also be substituted. Substituted by OH group or SH group.

R ^d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be chain (linear or branched), or cyclic, or any of linear, branched, and cyclic, or a combination of a chain group and a cyclic group. A base composed of bases. In the alkyl group of R ^d5 , methylene (-CH ₂ -) may be substituted with -O- or -CO-.

Specific examples of the alkyl group that may have a substituent in R ^d1 include groups represented by the following formulas. *Indicates bonding key.

Furthermore, in R ^d1 , the carbon number of the group which combined the aromatic hydrocarbon group and the alkanediyl group is preferably 7 to 33, more preferably 7 to 18, and even more preferably 7 to 12. This combined group may have one or more substituents, and examples of the substituents include the same groups as those exemplified as substituents that the aromatic hydrocarbon group and the alkyl group may have. Examples of the group represented by R ^d1 that is a combination of an aromatic hydrocarbon group and an alkanediyl group include an aralkyl group, and specifically, a group represented by the following formula. In the formula, * represents the bonding bond.

Among them, R ^d1 is preferably an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent.

The carbon number of the aromatic hydrocarbon group represented by R ^d2 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and terphenyl groups.

The number of carbon atoms in the heterocyclic group represented by R ^d2 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, and the like.

The number of carbon atoms in the alkyl group represented by R ^d2 is preferably 1 to 7, more preferably 1 to 5, and still more preferably 1 to 3. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group may be linear, branched, or cyclic, or may be a combination of a chain group and a cyclic group.

R ^d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, further preferably a chain alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

The carbon number of the aromatic hydrocarbon group represented by R ^d3 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and terphenyl, and preferred examples include phenyl and naphthyl.

The aromatic hydrocarbon group represented by R ^d3 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group. As the substituent, an aliphatic hydrocarbon group having 1 to 15 carbon atoms is preferred, and specific examples include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and Alkyl groups with 1 to 15 carbon atoms such as decyl; alkenyl groups with 1 to 15 carbon atoms such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl and decenyl wait.

The aromatic hydrocarbon group represented by R ^d3 may have an aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has a carbon number of 1 to 7. The aliphatic hydrocarbon group can be any of linear, branched, and cyclic, or can be a combination of a chain group and a cyclic group. base. In addition, the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group may be substituted with -O-, -CO- or -S-, and the methine group (-CH<) may be substituted with -N< .

Examples of the aliphatic hydrocarbon group include groups represented by the following formulas. In the formula, * represents the bonding bond.

Examples of the aromatic hydrocarbon group that may have a substituent in R ^d3 include groups represented by the following formulas, and the like. In the formula, * represents the bonding bond.

The number of carbon atoms in the heterocyclic group represented by R ^d3 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, and the like. The heterocyclic group represented by R ^d3 may have one or more substituents, and examples of the substituents include the same groups as those exemplified as the substituents that the aromatic hydrocarbon group represented by R ^d1 may have.

Among them, R ^d3 is preferably an aromatic hydrocarbon group with a substituent. As the substituent, it is preferably a chain alkyl group with 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms). The number of substituents is relatively small. Preferably, there are more than 2 and less than 5.

The carbon number of the aromatic hydrocarbon group represented by R ^d4 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, and the like, with phenyl and naphthyl being more preferred, and phenyl being even more preferred. In addition, the aromatic hydrocarbon group represented by R ^d4 may have one or more substituents. Examples of this substituent include the same substituents that the aromatic hydrocarbon group of R ^d1 may have.

The carbon number of the aliphatic hydrocarbon group represented by R ^d4 is preferably 1 to 13, more preferably 2 to 10, and even more preferably 4 to 9. Examples of the aliphatic hydrocarbon group represented by R ^d4 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl Alkyl groups such as tridecyl, tetradecyl and pentadecyl; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, Alkenyl groups such as decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl and pentadecenyl, etc. These aliphatic hydrocarbon groups may be chain (linear or branched), cyclic, or a combination of a chain group and a cyclic group. In the aliphatic hydrocarbon group of R ^d4 , methylene (-CH ₂ -) may be substituted with -O-, -CO- or -S-, and methine (-CH<) may be substituted with -PO ₃ <, The hydrogen atoms contained in the aliphatic hydrocarbon group may be substituted by OH groups.

Examples of the optionally substituted aliphatic hydrocarbon group represented by R ^d4 include groups represented by the following formulas, and the like. In the formula, * represents the bonding bond.

R ^d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group which does not have a substituent, and further preferably a branched chain alkyl group which does not have a substituent.

Examples of the compound (d1) include compounds represented by formula (d1), and specifically, compounds (d1-1) to (d1-67) having the substituents described in Tables 1 to 7. In Tables 1 to 7, * indicates a bonding key.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[Table 6]

[Table 7]

Among them, preferred are compounds represented by formula (d1-3) to formula (d1-6), compounds represented by formula (d1-18) to formula (d1-52), and compounds represented by formula (d1-55) Compounds, compounds represented by formula (d1-56), compounds represented by formula (d1-60), compounds represented by formula (d1-61), more preferably formulas (d1-3) to formula (d1-6 ), compounds represented by formula (d1-18) to formula (d1-41), more preferably compounds represented by formula (d1-24), formula (d1-36) to formula (d1-40 ) represented by the compound, Particularly preferred are compounds represented by formula (d1-24).

Compound (d1) can be produced by the production method described in Japanese Patent Publication No. 2014-500852, for example.

As the compound (d2), it is preferable that R ^d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent, R ^d2 is an alkyl group having 1 to 10 carbon atoms, and R ^d3 is an alkyl group having 6 to 15 carbon atoms which may have a substituent. 18 aromatic hydrocarbon group and R ^d4 is an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent. More preferably, R ^d1 represents a methyl group, an ethyl group or a propyl group, and R ^d2 represents a methyl group, an ethyl group or a Propyl and R ^d3 represent a methyl-substituted phenyl group, and R ^d4 is a methyl, ethyl or propyl group. More preferably, R ^d1 and R ^d2 are methyl, R ^d3 is o-tolyl, and R ^d4 is Ethyl compounds.

The compound (d3) is preferably a compound in which R ^d1 is an optionally substituted alkyl group having 1 to 15 carbon atoms, and R ^d2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms. More preferably, R ^d1 is a hexyl group and R Compounds in which ^d2 is phenyl.

Examples of such O-benzyl oxime compounds include N-benzyloxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine and N-benzyloxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine. Benzyloxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylmercaptophenyl)-3- Cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methyl Benzyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3 ,3-Dimethyl-2,4-dioxolylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyl Oxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyl Cyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-ylidene Amines etc. Commercially available products such as Irgacure OXE01, OXE02, and OXE03 (the above, manufactured by BASF Co., Ltd.) and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used. If these O-acyl oxime compounds are used, a blue color filter excellent in photolithography performance tends to be obtained.

The phenylalkyl ketone compound is a compound having a structure represented by formula (d4) or a structure represented by formula (d5). *Indicates bonding key. In these structures, the benzene ring may have a substituent.

Examples of compounds having a structure represented by formula (d4) include: 2. Methyl-2-morpholinyl-1-(4-methylmercaptophenyl)propan-1-one, 2-dimethylamine Base-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- 1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. Commercially available products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Co., Ltd.) can also be used.

Examples of compounds having a structure represented by formula (d5) include: 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-( 2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomers, α,α-diethoxyacetophenone, benzyldimethyl ketal, etc.

In terms of sensitivity, the phenylalkyl ketone compound is preferably a compound having a structure represented by formula (d4).

Examples of the biimidazole compound include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-bis Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, Japanese Patent Application Laid-Open Publication No. Sho 62-174204, etc.), imidazole compounds in which the phenyl groups at the 4, 4', 5, 5'-positions are substituted with alkoxycarbonyl groups (for example, see Japanese Patent Application Laid-Open No. 7-10913, etc.), etc. Among them, compounds represented by the following formula or mixtures thereof are preferred.

Examples of triazine compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) base)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(5-Methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene base]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1 ,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. .

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

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, and methyl o-benzoyl benzoate. , 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)diphenyl Methyl ketone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2- Chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably combined with the polymerization starting aid (D1) described below (especially is an amine) used in combination.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 3 to 25 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). , more preferably 5 parts by mass to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be shortened, so the productivity of the blue color filter tends to be improved.

[5]Polymerization starting aid (D1)

The polymerization starting aid (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound started by the polymerization initiator. When the polymerization initiating aid (D1) is included, it can be used in combination with the polymerization initiator (D).

Examples of the polymerization starting aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like. Among them, thioxanthone compounds are preferred. Two or more polymerization starting aids (D1) may be used in combination.

Examples of the amine compound include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethyl Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis (ethylmethylamino)benzophenone and the like, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of alkoxyanthracene compounds include: 9,10-dimethoxyanthracene, 2-ethyl 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl Base-9,10-dibutoxyanthracene, etc.

Examples of the thioxanthone compound include: 2-isopropylthianthrone, 4-isopropylthianthrone, 2,4-diethylthianthrone, and 2,4-dichlorothianthone. Anthrone, 1-chloro-4-propoxythiaxanthone, etc.

Examples of carboxylic acid compounds include: phenylthioglycolic acid, methylphenylthioglycolic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylmercaptoacetic acid, and methoxyphenylmercaptoacetic acid. Acetic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylmercaptoacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine , naphthoxyacetic acid, etc.

The content of the polymerization starting aid (D1) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). share. When the content of the polymerization starting aid (D1) is within the above range, a blue pattern can be formed with further high sensitivity, and the productivity of the blue color filter tends to be improved.

[6] Thiol compound (T)

The blue curable resin composition of the present invention may also contain one or more thiol compounds (T). The thiol compound (T) can be used particularly preferably when the polymerization initiator (D) is an oxime-based compound such as an O-acyl oxime compound and/or a biimidazole compound. The thiol compound (T) is a compound having at least one thiol group (-SH) in the molecule. The thiol compound (T) is preferably a compound having one mercapto group in the molecule.

Examples of compounds having one mercapto group in the molecule include: 2-mercapto group Oxazole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptonicotinic acid, 2-mercaptopyridine, 2-mercaptopyridin-3-ol , 2-mercaptopyridine-N-oxide, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amino-2-mercaptopyrimidine, 6 -Amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2,4- Diamino-6-mercaptopyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, 4-hydroxy-2-mercapto-6-methylpyrimidine, 4- Hydroxy-2-mercapto-6-propylpyrimidine, 2-mercapto-4-methylpyrimidine, 2-mercaptopyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-mercaptoimidazole, 2-mercapto-1-methylimidazole, 4-amino-3-hydrazino-5-mercapto-1,2,4-tri Azole, 3-amino-5-mercapto-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1, 2,4-triazole-3-thiol, 3-mercapto 1H-1,2,4-triazole-3-thiol, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-Amino-1,3,4-thiadiazole-2-thiol, 2,5-dimercapto-1,3,4-thiadiazole, (furan-2-yl)methylthiol, 2- Mercapto-5-thiazolidinone, 2-mercaptothiazoline, 2-mercapto-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-Mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 6-amino-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 6-ethyl Oxy-2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercaptonaphthoimidazole, 2-mercaptonaphthoxazole, 3-mercapto-1,2,4-triazole, 4-Amino-6-mercaptopyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-mercaptopurine and 4-mercapto-1H-pyrazolo[2,4- d]pyrimidine etc.

Examples of compounds having two or more mercapto groups in the molecule include: hexanedithiol, decanedithiol, 1,4-bis(methylmercapto)benzene, butylene glycol bis(3-mercaptopropionic acid) ester), butylene glycol bis(3-mercaptoacetate), ethylene glycol bis(3-mercaptoacetate), trimethylolpropane tris(3-mercaptoacetate), butylene glycol bis(3-mercaptoacetate) -Mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptoacetate), trihydroxyethyl tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate) and 1,4-bis(3-mercaptobutyloxy)butane wait.

Relative to 100 parts by mass of the polymerization initiator (D), the content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 10 parts by mass. 40 parts by mass. When the content of the thiol compound (T) is within the above range, the sensitivity tends to be high and the developability tends to be good.

〔7〕Solvent (E)

The blue curable resin composition of the present invention preferably contains one or more solvents (E). Examples of the solvent (E) include ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), Ketone solvents other than ester solvents (solvents including -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, Isopropyl butyrate, Ethyl butyrate, Butyl butyrate, Methyl pyruvate, Ethyl pyruvate, Propyl pyruvate, Methyl acetate acetate, Ethyl acetate acetate, Ring Hexanol acetate and γ-butyrolactone, etc.

Examples of ether solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Alcohol 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, diglyme , diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenylethyl ether and methyl anisole, etc.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyethyl acetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropylpropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate acid ester and dipropylene glycol methyl ether acetate, etc.

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

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, and the like. Examples of amide solvents include: N, N- Dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, etc.

In terms of coating properties and drying properties, the solvent (E) preferably contains an organic solvent having a boiling point at 1 atm of 120° C. or more and 180° C. or less. Among them, the solvent (E) is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, and diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutylacetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N -At least one of the group consisting of dimethylformamide, more preferably one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3- At least one of the group consisting of methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate.

In the blue curable resin composition, the content of the solvent (E) is preferably 70 mass% to 95 mass%, more preferably 75 mass% to 92 mass%. In other words, the solid content of the blue curable resin composition is preferably 5% to 30% by mass, more preferably 8% to 25% by mass. When the content of the solvent (E) is within the above range, the flatness during coating becomes good, and the color density does not become insufficient when forming a blue color filter, and the display characteristics tend to become good.

〔8〕Leveling agent (F)

The blue curable resin composition of the present invention may contain one or more leveling agents (F). Examples of the leveling agent (F) include silicone surfactants (not having fluorine atoms), fluorine surfactants, silicone surfactants having fluorine atoms, and the like. These may have a polymerizable group in a side chain.

Examples of silicone-based surfactants include those having a siloxane bond in the molecule. Surfactants, etc. Specifically, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (trade name; Toray Dow Corning) ), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Japanese Momentive High-tech materials (Momentive Performance Materials Japan) Co., Ltd.), etc.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac )F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Co., Ltd.), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop ) EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Research Institute Co., Ltd.), etc.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (DIC). (stock) manufacturing), etc.

In the blue curable resin composition, the content of the leveling agent (F) is usually 0.001 mass % or more and 0.6 mass % or less, preferably 0.002 mass % or more and 0.4 mass % or less, more preferably 0.005 mass % or more. And less than 0.2% by mass. Furthermore, this content does not include the content of the pigment dispersant.

〔9〕Antioxidant (G)

From the viewpoint of improving the heat resistance and light resistance of the colorant (A), the blue curable resin composition preferably contains an antioxidant. The antioxidant is not particularly limited as long as it is an antioxidant commonly used in industry, and phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc. can be used. Two or more types of antioxidants may be used.

Examples of phenolic antioxidants include: Irganox 1010 (pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], BASF) (manufactured by BASF Co., Ltd.), Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, BASF Co., Ltd. ), Irganox 1330 (Irganox 1330: 3,3',3",5,5',5"-hexa-tertiary butyl -a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Co., Ltd.), Irganox 3114 (1, 3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, BASF (manufactured by BASF Co., Ltd.), Irganox 3790 (1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)- 1,3,5-Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 1035 (Irganox 1035: thiodiethylene bis[ 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd.), Irganox 1135 (Irganox 1135: phenylpropionic acid, 3, 5-Bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF Co., Ltd.), Irganox 1520L (Irganox 1520L: 4,6 -Bis(octylthiomethyl)-o-cresol, manufactured by BASF Co., Ltd.), Irganox 3125 (manufactured by BASF Co., Ltd.), Irganox 565 : 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, BASF ( Co., Ltd.), Adekastab AO-80 (Adekastab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanol) (Carboxyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd.), Sumilizer BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd. Cyanox 1790 (manufactured by Cytec Co., Ltd.), Cyanox 1790 (manufactured by Cytec Co., Ltd.), Vitamin E (manufactured by Eisai Co., Ltd.), etc.

Examples of phosphorus antioxidants include: Igrafos 168: Tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Co., Ltd.), Igrafos 12: tris[2-[[2,4,8, 10-Tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, manufactured by BASF Co., Ltd.), Igrafos 38 (Igrafos 38: Bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, manufactured by BASF Co., Ltd.) , Adekastab 329K (manufactured by ADEKA Co., Ltd.), Adekastab PEP36 (manufactured by ADEKA Co., Ltd.), Adekastab (Adekastab) PEP-8 (manufactured by ADEKA Co., Ltd.), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (Weston 618, GE Company Manufactured), Weston 619G (Weston 619G, manufactured by GE Company), Ultranox 626 (Ultranox 626, manufactured by GE Company) and Sumilizer GP (Sumilizer GP, 6-[3-(3-No. Tributyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]di Oxaphospine) (manufactured by Sumitomo Chemical Co., Ltd.), etc.

Examples of sulfur-based antioxidants include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, or distearyl thiodipropionate, and tetrahydrofuran thiodipropionate. [Methylene (3-dodecylthio)propionate] β-alkylmercaptopropionate compounds of polyhydric alcohols such as methane, etc.

In the blue curable resin composition, the content of the antioxidant (G) is usually 0.01 mass % or more and 5 mass % or less, preferably 0.04 mass % or more and 3 mass % or less, more preferably 0.07 mass % or more and 3 mass % or less. 1% by mass or less.

〔10〕Other ingredients

The blue curable resin composition of the present invention may contain one or more fillers, polymer compounds other than resin (B), adhesion accelerator, ultraviolet absorber, anti-aggregation agent, organic acid, and organic amine as necessary. Compounds, hardeners and other additives.

Examples of fillers include glass, silica, alumina, and the like. Examples of polymer compounds other than resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and the like.

Examples of the adhesion accelerator include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, and N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-hydride Glyceroxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, etc.

Examples of ultraviolet absorbers include benzotriazole compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; 2-hydroxy-4 -Octyloxybenzophenone and other benzophenone compounds; 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and other benzene compounds Formic acid ester compounds; triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc. Examples of anti-aggregation agents include sodium polyacrylate and the like.

Organic acids can be used to adjust developability, specifically: Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, caprylic acid and other aliphatic monocarboxylic acids; oxalic acid, malonic acid, succinic acid, glutaric acid , adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid (Brassylic acid), methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, Methyl succinic acid, tetramethyl succinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid and other aliphatic dicarboxylic acids; 1, Aliphatic tricarboxylic acids such as 2,3-tricarballylic acid, aconitic acid, and camphoronic acid; benzoic acid, methylbenzoic acid, cumic acid, 2 , 3-dimethylbenzoic acid (hemellitic acid), 3,5-dimethylbenzoic acid (mesitylenic acid) and other aromatic monocarboxylic acids; phthalic acid, isophthalic acid, terephthalic acid and other aromatic dicarboxylic acids; Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, 1,2,3,5-mellophanic acid (mellophanic acid), and pyromellitic acid.

Examples of organic amine compounds include: n-propylamine, isopropylamine, n-butylamine, isobutylamine, second-butylamine, third-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, and n-nonylamine. , n-decylamine, n-undecylamine, n-dodecylamine and other monoalkylamines; cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine and other monocyclic amines Alkylamines; methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, Diisopropylamine, di-n-butylamine, diisobutylamine, di-second-butylamine, di-tert-butylamine, di-n-pentylamine, di-n-hexylamine and other dialkylamines; methylcyclohexylamine , monoalkyl monocycloalkylamines such as ethylcyclohexylamine; bicycloalkylamines such as dicyclohexylamine; dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, Diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-second-butylamine, tri- Trialkylamines such as tert-butylamine, tri-n-pentylamine, and tri-n-hexylamine; dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine; methyldicyclohexylamine , ethyldicyclohexylamine, tricyclohexylamine and other monoalkyldicycloalkylamines; 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4- Monoalkanolamines such as amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol; monocyclic alkanolamines such as 4-amino-1-cyclohexanol; Diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine and other dialkanolamines; two (4 -Cyclohexanol)amine and other dicycloalkanolamines; triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, triisopropanolamine -Trialkanolamines such as n-hexanolamine; tricycloalkanolamines such as tris(4-cyclohexanol)amine; 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4- Amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2- Propylene glycol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol and other aminoalkanediols (alkanediol); 4-amino-1,2-cyclohexane Amino cycloalkane diols such as diol and 4-amino-1,3-cyclohexanediol; cycloalkanone methanols containing amine groups such as 1-aminocyclopentanonemethanol and 4-aminocyclopentanonemethanol. ;1-aminocyclohexanonemethanol, 4-aminocyclohexanonemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylamino cyclohexanemethanol, 4-diethylaminocyclohexanemethanol and other cycloalkane hydroxymethanols containing amine groups; β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid Acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1- Aminocarboxylic acids such as aminocyclohexanecarboxylic acid and 4-aminocyclohexanecarboxylic acid; aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, p-n-propylaniline , p-isopropylaniline, p-n-butylaniline, p-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, Aromatic amines such as p-methyl-N,N-dimethylaniline; o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylamine Aminobenzyl alcohols such as benzyl alcohol; aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol; m-aminobenzoic acid, p-aminophenol Aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and other aminobenzoic acids.

Examples of the curing agent include compounds that react with carboxyl groups in the resin (B) by heating to cross-link the resin (B), compounds that can be polymerized alone to cure the blue color filter, and examples of the curing agent include cyclic compounds. Oxygen compounds, oxetane compounds, etc. Only one type of hardening agent may be used, or two or more types of hardening agents may be used in combination.

Examples of the epoxy compound include bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, novolac-type epoxy resin, and others. Epoxy resins such as aromatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxidized oils, or bromines of these epoxy resins Aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, epoxides of (co)polymers of butadiene, (co)polymers of isoprene ) epoxide of polymer, (co)polymer of glycidyl (meth)acrylate, triglycidyl isocyanurate, etc. Examples of commercially available epoxy resins include: o-cresol novolac type epoxy resin, "Sumiepoxy (registered trademark) ESCN-195XL-80" (manufactured by Sumitomo Chemical Co., Ltd.), etc. .

Examples of the oxetane compound include: dioxetane carbonate, xylylenedioxetane, dioxetane adipate, dioxetane terephthalate, Cyclohexanedicarboxylic acid dioxetane, etc.

When the blue curable resin composition of the present invention contains an epoxy compound, an oxetane compound, etc. as a curing agent, it may also contain an epoxy group of the epoxy compound or an oxetane compound. A compound that undergoes ring-opening polymerization of an oxetane skeleton. Examples of the compound include polycarboxylic acids, polycarboxylic anhydrides, acid products Biopharmaceuticals, etc.

Examples of polycarboxylic acids include: 3,4-dimethylphthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4, Aromatic polycarboxylic acids such as 4'-benzophenonetetracarboxylic acid; aliphatic polycarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid; hexahydrophthalic acid, 3,4-dimethyl Tetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetricarboxylic acid Alicyclic polycarboxylic acids such as alkanetetracarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of polycarboxylic anhydrides include aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3',4,4'-benzophenone tetracarboxylic dianhydride. ; Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, 1,2,3-propanetricarboxylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic acid dicarboxylic acid anhydride and other aliphatic polycarboxylic acid anhydrides; hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4- Cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-norbornene-2,3-dicarboxylic anhydride, nadic acid anhydride Such as alicyclic polycarboxylic acid anhydrides; carboxylic acid anhydrides containing ester groups such as ethylene glycol bis-trimellitic acid anhydride and glycerol trimellitic anhydride.

As the carboxylic acid anhydride, a commercial product that is an epoxy resin hardener can also be used. Examples of epoxy resin hardeners include the brand name "ADEKA" Hardener) (registered trademark) EH-700" (manufactured by ADEKA Co., Ltd.), brand name "Rikacid (registered trademark) HH" (manufactured by New Nippon Rika Co., Ltd.), brand name "MH-700" (manufactured by New Japan Physical & Chemical Co., Ltd.), etc.

Examples of acid generators include 4-hydroxyphenyldimethylsulfonate p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonate hexafluoroantimonate, and 4-acetyloxyphenyldimethylsulfonate. p-Toluenesulfonate, 4-acetyloxyphenyl. methyl. Benzylsonium hexafluoroantimonate, triphenylsonium p-toluenesulfonate, triphenylsonium hexafluoroantimonate, diphenylphosphonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate, etc. salt, or nitrobenzyl toluene sulfonate, benzoin toluene sulfonate, etc.

<Production method of blue curable resin composition>

The blue curable resin composition of the present invention can be obtained by combining the colorant (A), the resin (B), the polymerizable compound (C) and the polymerization initiator (D), and optionally the solvent (E), sulfur The alcohol compound (T), leveling agent (F), polymerization starting aid (D1), antioxidant (G), and other ingredients are mixed and prepared.

<Blue color filter and manufacturing method thereof, blue color filter and display device>

The blue curable resin composition of the present invention is useful as a material for blue color filters. In addition, a blue color filter formed from the blue curable resin composition of the present invention also falls within the scope of the invention of this application. Blue color filters can also create blue patterns.

Examples of a method for producing a blue pattern from the blue curable resin composition of the present invention include photolithography, inkjet, printing, etc. Preferably, photolithography is used Law. Photolithography is a method in which a blue curable resin composition is applied to a substrate, dried to form a blue composition layer, and the blue composition layer is exposed and developed through a light mask. In the photolithography method, by not using a photomask during exposure and/or not performing development, a blue coating film that is a cured product of the blue composition layer can be formed. The blue pattern or blue coating film formed from the blue curable resin composition of the present invention is the blue color filter of the present invention. The blue color filter of the present invention can typically be used as a blue pixel.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass with a silica-coated surface can be used; or polycarbonate, polymethyl methacrylate, poly(methylmethacrylate), etc. Resin plates such as ethylene terephthalate; silicon; aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The photolithography method is used to form each color pixel, which can be performed under known or customary equipment or conditions. For example, it can be produced in the following manner. First, a blue curable resin composition is applied to a substrate, and the volatile components such as solvent are removed by heating and drying (prebaking) and/or drying under reduced pressure to obtain a smooth blue composition. layer. Examples of coating methods include spin coating, slit coating, slit and spin coating, and the like.

The temperature during heat drying is preferably 30°C to 120°C, more preferably 50°C to 110°C. In addition, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When drying under reduced pressure is performed, it is preferably carried out under a pressure of 50 Pa to 150 Pa and a temperature range of 20°C to 25°C. Blue composition layer film The thickness is not particularly limited, as long as it is appropriately selected according to the film thickness of the target blue color filter.

Next, the blue composition layer is exposed through a photomask for forming a target blue pattern. The pattern on this photomask is not particularly limited, and a pattern corresponding to the intended use can be used. As a light source used for exposure, a light source that generates light with a wavelength of 250 nm to 450 nm is preferred. For example, for light less than 350nm, a filter can be used to cut off the wavelength range, or for light near 436nm, 408nm, and 365nm, a bandpass filter can be used to selectively extract light in these wavelength ranges. . Specifically, examples of the light source include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.

During exposure, in order to uniformly irradiate the entire exposure surface with parallel light, or to accurately align the mask and the substrate on which the blue composition layer is formed, it is preferable to use a mask aligner, a stepper, etc. for exposure. device.

The exposed blue composition layer is developed by contacting a developer to form a blue pattern on the substrate. By development, the unexposed portion of the blue composition layer is dissolved in the developer and removed.

The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 mass% to 10 mass%, more preferably 0.03 mass% to 5 mass%. Furthermore, the developer may contain a surfactant.

The development method may be any of liquid coating method, dipping method, spray method, etc. Furthermore, the substrate can be tilted to any angle during development. After development, it is better to carry out Wash.

Furthermore, it is preferable to post-bake the obtained blue pattern. The post-baking temperature is preferably 150°C~250°C, and more preferably 160°C~235°C. The post-baking time is preferably 1 minute to 120 minutes, more preferably 10 minutes to 60 minutes.

Since the thickness of the obtained blue coating affects adjacent pixels, it is preferably as thin as possible. Particularly in the case of a thick film, when manufacturing a liquid crystal panel, light from the light source may leak through pixels of two or more colors, and there is a concern that the vividness of the colors may be lost when the panel is viewed from an oblique direction. The film thickness of the blue coating film after post-baking is generally preferably 3 μm or less, more preferably 2.8 μm or less. The lower limit of the film thickness of the blue coating film is not particularly limited, but is usually 1 μm or more, and may be 1.5 μm or more. The blue coating film exhibits excellent developability and is therefore excellent as a material for a blue color filter.

The higher the brightness of the blue coating film, the better, preferably 8 or more, more preferably 9 or more, and the upper limit is not particularly limited, but is usually 15 or less.

The blue color filter of the present invention is useful as a blue color filter used in display devices (liquid crystal display devices, organic electroluminescence (EL) devices, electronic paper, etc.) and solid-state imaging devices.

[Example]

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to these examples. In the examples, % and parts indicating content or usage amount are based on mass unless otherwise stated.

<Synthesis Example 1: Pigment Dispersion Liquid (A1)>

Mix and fully disperse the pigment using a bead mill, thereby obtaining a pigment dispersion liquid (A1) containing C.I. Pigment Blue 15.

<Synthesis Example 2: Pigment Dispersion Liquid (A2)>

Mix and fully disperse the pigment using a bead mill, thereby obtaining a pigment dispersion (A2) containing C.I. Pigment Blue 15:6.

<Synthesis Example 3: Pigment Dispersion (A3)>

Mix and fully disperse the pigment using a bead mill, thereby obtaining a pigment dispersion (A3) containing C.I. Pigment Blue 15:3.

<Synthesis Example 4: Pigment Dispersion Liquid (A4)>

Mix and use a bead mill to fully disperse the pigment to obtain C.I. Pigment blue 15:4 pigment dispersion (A4).

<Synthesis Example 5: Pigment Dispersion Liquid (A5)>

Mix and fully disperse the pigment using a bead mill, thereby obtaining a pigment dispersion (A5) containing C.I. Pigment Blue 16.

<Synthesis Example 6: Pigment Dispersion Liquid (A6)>

Mix and fully disperse the pigment using a bead mill, thereby obtaining a pigment dispersion (A6) containing C.I. Pigment Violet 23.

<Synthesis Example 7: Preparation of xanthene dye (A7)>

20 parts of the compound represented by the formula (1a) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the obtained The solution was stirred at 110°C for 6 hours.

After the obtained reaction liquid was cooled to room temperature, it was added to a mixture of 800 parts of water and 50 parts of 35% by weight hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. As a result, crystals were precipitated. The precipitated crystal is obtained as a residue of suction filtration and then dried to obtain the compound represented by the formula (1-24). Hereinafter, this compound is called xanthene dye (A7).

<Synthesis Example 8: Preparation of Resin (B)>

In a flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen gas is sufficiently circulated to set it to a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate are added. , heating to 70°C while stirring. Next, a solution was prepared by dissolving 60 parts of methacrylic acid and 240 parts of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate in 140 parts of 3-methoxybutyl acetate. The solution was added dropwise from a funnel to a flask insulated at 70°C over 4 hours.

On the other hand, another dropping funnel was used to dissolve 30 parts of 2,2-azo (2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate over 4 hours. The mixed solution was added dropwise into the flask. After the dropwise addition, the temperature was maintained for 4 hours, and then cooled to room temperature to obtain a resin solution with a solid content of 32.6% by weight and an acid value of 110 mg-KOH/g (in terms of solid content). The weight average molecular weight (Mw) of the resin (B) contained in the obtained resin solution was 13,400, and the molecular weight distribution was 2.50.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin (B) were measured using the gel permeation chromatography (Gel Permeation Chromatography, GPC) method under the following conditions. The ratio (Mw/Mn) of the polystyrene-reduced weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained under the following conditions was defined as the molecular weight distribution.

Device: HLC-8120GPC (manufactured by TOSOH Co., Ltd.)

Column: TSK-GELG2000HXL

Tube string temperature: 40℃

Solvent: THF (tetrahydrofuran, tetrahydrofuran)

Flow rate: 1.0mL/min

Solid content concentration of the liquid to be tested: 0.001 mass%~0.01 mass%

Injection volume: 50μL

Detector: RI

Calibration standard materials: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH Co., Ltd.)

<Example 1 to Example 5 and Comparative Example 1 to Comparative Example 5>

(1) Preparation of blue curable resin composition

Each of the pigment dispersions (A1) to pigment dispersions (A6), the xanthene dye (A7), and C.I. Acid Red 52 (manufactured by Wako Pure Chemical Industries, Ltd.) obtained in the synthesis examples 1 to 6 were ) (A8), C.I. basic violet 10 (manufactured by Wako Pure Chemical Industries, Ltd., rhodamine B) represented by the following formula (A9), containing the resin (B) obtained in Synthesis Example 8 The resin solution, polymerizable compound (C), polymerization initiator (Da), polymerization initiator (Db), thiol compound (T), and leveling agent (F) were prepared in amounts described in Table 8 Mix to obtain a blue curable resin composition.

Furthermore, when preparing a blue curable resin composition, propylene glycol monomethyl ether acetate is mixed so that the color material concentration in the solid content of the blue curable resin composition becomes 30% by mass. The unit of the blending amount of each component in Table 8 is "mass parts", and the blending amount is converted in terms of solid content. Details of each ingredient are as follows.

[Polymerizable compound and polymerization initiator used]

Polymerizable compound (C): pentaerythritol triacrylate (trade name "A-TMM-3LM-N" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), polymerization initiator (Da): a compound represented by the following formula.

Polymerization initiator (Db): 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxy) Phenyl)-4,5-diphenyl-1,1'-biimidazole (trade name "TCDM" manufactured by CHEMBRIDGE INTERNATIONAL CORPORATION), thiol compound (T): 2-mercaptobenzo Thiazole (trade name "Sanceler M" manufactured by Sanshin Chemical Industry Co., Ltd.), leveling agent (F): polyether modified silicone oil (trade name manufactured by Toray Dow Corning Co., Ltd. Trade name "Toray silicone SH8400").

(2) Production of blue coating film

A blue curable resin composition was applied on a 2-inch square glass substrate ("Eagle XG" manufactured by Corning Corporation) by spin coating, and then prebaked at 100°C for 3 minute. After cooling, the blue curable resin was coated with an exposure machine ("TME-150RSK" manufactured by Topcon Co., Ltd.) in an atmospheric environment at an exposure dose of 80 mJ/cm ² (based on 365 nm). The substrate of the composition is irradiated with light. Thereafter, post-baking was performed at 230° C. for 30 minutes in an oven to obtain a blue coating film.

(3)Color evaluation

The spectrum of the obtained blue coating film was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the CIE XYZ colorimetric system was measured using the characteristic function of the C light source. The xy chromaticity coordinates (x, y) and the tristimulus value Y. The results are shown in Table 9.

In Examples 1 to 5 and Comparative Examples 1 to 5, y is unified to 0.095.

In Examples 1 to 5, compared with Comparative Example 1 showing the same x and y, high brightness was obtained. In addition, in Comparative Example 2, although high brightness was obtained, only high x was obtained compared with Examples 1 to 5.

Claims (3)

A blue curable resin composition, which contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) contains C.I. Pigment Blue 15 , and red dye or purple dye, the red dye or purple dye contained in the colorant (A) is a compound with a xanthene skeleton, and the content of the compound with a xanthene skeleton is in the colorant (A) 0.1 mass% to 5 mass% in 100 mass%. A blue color filter is formed from the blue curable resin composition described in item 1 of the patent application. A display device containing the blue color filter as described in item 2 of the patent application scope.