TW201922945A - Blue curable resin composition, blue color filter, and display device including same - Google Patents

Abstract

To provide a blue curable resin composition having high brightness, in which x in the xy chromaticity diagram thereof in the XYZ color system is relatively low, a blue color filter formed from the blue curable resin composition, and a display device including the blue color filter. A blue curable resin composition including a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), the colorant (A) including C.I. pigment blue 15 and a red dye or violet 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 including the same.

In recent years, the demand for a liquid crystal display device with a wide displayable color reproduction range has increased.
Patent Document 1 proposes a composition including a combination of CI pigment blue 15 and CI pigment violet 23. Patent Document 2 proposes a composition containing CI Pigment Blue 15: 6 and a red dye.
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-316388
[Patent Document 2] Japanese Patent Laid-Open No. 2010-32999

[Problems to be Solved by the Invention]
An object of the present invention is to provide a blue curable resin composition having a low x and high brightness in an xy chromaticity diagram in the XYZ color system in order to obtain a display device with a wide displayable color reproduction range. A blue color filter formed of a flexible resin composition, and a display device including the blue color filter.
[Means for solving problems]

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

[1] A blue curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) includes CI Pigment blue 15, with red dye or purple dye.
[2] The blue curable resin composition according to [1], wherein the red dye or the purple dye contained in the colorant (A) is a compound having an xanthracene skeleton.
[3] The blue curable resin composition according to [2], wherein the content of the compound having a xanthracene skeleton in the colorant (A) is from 0.1% by mass to 25% by mass.
[4] A blue color filter formed of 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].
[Effect of the invention]

According to the blue curable resin composition of the present invention, a blue color filter having low x and high brightness in the xy chromaticity diagram in the XYZ color system and a display device including the same can be provided.

<Blue hardening 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 CI Pigment Blue 15, and Red dye or purple dye.
According to a blue curable resin composition containing CI Pigment Blue 15 and a specific combination with a red dye or a purple dye, x in the xy chromaticity diagram in the XYZ color system can be reduced, and brightness can be improved.
The x of the xy chromaticity diagram in the XYZ color system (hereinafter, also referred to as x) refers to the XYZ color system based on the international notation formulated by the International Commission for Illumination (CIE) in 1931. X coordinate (x) of blue (B) in xy chromaticity coordinates (x, y).
When the y (hereinafter, also referred to as y) of the xy chromaticity diagram in the XYZ color system is the same, the lower the x, the higher the chroma, and the displayable color reproduction range of the display device changes. Wide tendency.
The brightness refers to the stimulus value Y in the XYZ color system, and the larger the Y value, the higher the brightness tends to be.
The chromaticity coordinates and brightness of the xy chromaticity diagram in the XYZ color system are measured in accordance with "(4) chromaticity evaluation" described in the Example column described later.
In addition, in the present specification, the compounds exemplified as each component may be used singly or in combination of a plurality of types unless otherwise specified.

[1] Colorant (A)
In the blue curable resin composition of the present invention, the colorant (A) contains CI Pigment Blue 15, and a red dye or a purple dye. Since the blue curable resin composition contains the colorant (A), it is possible to reduce x in the xy chromaticity diagram in the XYZ color system, and to increase the brightness. Therefore, it is useful as a material for a blue color filter.
CI Pigment Blue 15 is a compound classified as a blue pigment in the dye index (CI: Color Index, published by The Society of Dyers and Colourists).

The blue curable resin composition is one having a maximum absorption wavelength between 580 nm and 650 nm.

Any one of the red dye and the violet 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 CI Pigment Blue 15 With red dye and / or purple dye.

The red dye refers to a dye having a maximum absorption wavelength from 480 nm to 560 nm, and the purple dye refers to a dye having a maximum absorption wavelength from 560 nm to 580 nm.

As the red dye and the violet dye, one or two or more conventionally known red dyes and violet dyes can be used, respectively. From the viewpoint that the brightness can be increased, the red dye and the purple dye are each preferably a compound having a xanthracene skeleton (hereinafter, also referred to as "xanthracene dye").

The xanthracene dye is preferably a compound represented by the following formula (1) [hereinafter, also referred to as "xanthene dye (1)"]. The xanthracene dye (1) may be used alone or in combination of two or more.

[In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, —R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or R ¹ and R ² and R ³ and R ⁴ are formed together. comprising a ring nitrogen atom; a hydrogen atom contained in the aromatic hydrocarbon group may be a halogen ^{atom, -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; examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an 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 of 0 to 5; when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different from each other;
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
M ⁺ means ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ ;
X represents a halogen atom; examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;
a represents 0 or 1;
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group or halogen atom having 6 to 10 carbon atoms. -CH ₂ -contained in the saturated hydrocarbon group may be -S -, - O -, - CO- or -NR ¹¹ - substituted; R ¹¹ represents a hydrogen atom, the carbon number of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10; R ¹¹ to When there are multiple, all or part of these may be the same;
R ⁹ and R ¹⁰ each 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 substituted with -OH or a halogen atom. The saturated aliphatic hydrocarbon group contains -CH ₂ -may be substituted by -S-, -O-, -CO-, -NH-, or -NR ^8- ; R ⁹ and R ¹⁰ may be bonded to each other to form a 3-membered ring to 10 members containing a nitrogen atom. A ring heterocyclic ring; examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ in the formula (1) include phenyl, tolylmethyl, xylyl, mesityl, and propylbenzene. And butylphenyl.
Formula (1) R ¹ ~ R ^4, the carbon number of the monovalent aromatic hydrocarbon group having 6 to 10 is preferably selected from the group consisting of having _{^{-SO 3 -, -SO 3 H,}} -SO 3 - M + and -SO ₂ At least one selected from the group consisting of NR ⁹ R ¹⁰ has a substituent, and more preferably has at least one selected from the group consisting of -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R ¹⁰ . As in this case -SO ₃ ^- M ^+, 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 and the ring formed by R ³ and R ⁴ include, for example, the following rings. In the following rings, * indicates a bond.

Examples of R ⁸ to R ¹¹ in formula (1) as 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, cetyl, eicosyl, etc. Alkyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other cycloalkyl groups having 3 to 20 carbon atoms.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ and the aromatic hydrocarbon group having 6 to 10 carbon atoms in which a hydrogen atom may be substituted include phenyl, tolylmethyl, xylyl, and mesity Tolyl, propylphenyl, and butylphenyl. 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, * indicates 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 a group represented by the following formula. In the following bases, * indicates a bond.

In the formula, X ⁰ and X ² each 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, phenylethyl, and phenylbutyl.

M ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and is preferably ⁺ N (R ¹¹ ) ₄ . ⁺ N (R ¹¹ ) _{4 is} preferably a monovalent saturated hydrocarbon group having at least two of four R ¹¹ having 5 to 20 carbon atoms. The total carbon number of the four R ¹¹ is preferably 20 to 80, and more preferably 20 to 60.

The xanthracene dye (1) is preferably a compound represented by the 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, and the hydrogen atom contained in the aromatic hydrocarbon group may pass through —SO ₃ ^- , -SO ₃ ^- M ^{a +} , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .
X represents a halogen atom; examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;
a1 means 0 or 1.
m1 represents an integer of 0 to 5; when m1 is an integer of 2 or more, a plurality of 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 - M}} a +, -SO 3 H or SO ₂ NHR ^26;
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms;
Four R ²⁷ each independently represent a monovalent saturated hydrocarbon group or benzyl group having 1 to 20 carbon atoms]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ in formula (2) include the same groups as those listed 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 a hydrogen atom contained in the aromatic hydrocarbon group is substituted. , substitution group is _{^{-SO 3 -, -SO 3 - M}} +, -SO 3 H, -SO 3 R 26 or -SO ₂ NHR ^26. Further, more preferably R ²¹ and R ²³ is a hydrogen atom, and R ²² and R ²⁴ is a divalent aromatic hydrocarbon group having a carbon number of 6 to 10, an aromatic hydrocarbon group and the hydrogen atom may be contained in the -SO ₃ ^- M ⁺ or -SO ₂ NHR ^{26 is} 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 formula (2) include the same groups as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ . -R ²⁶ in R ²¹ to R ²⁴ in formula (2) is preferably a hydrogen atom, a methyl group, or an ethyl group independently of each other.
Formula (2), and -SO ₃ R ²⁶ is -SO ₂ NHR ²⁶ R ^26, preferably branched chain alkyl group having a carbon number of 3 to 20 carbon atoms, more preferably branched having 6 to 12 The alkyl group is more preferably 2-ethylhexyl.
M ^{a +} is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ . ⁺ N (R ²⁷ ) _{4 is} preferably a monovalent saturated hydrocarbon group in which at least two of the four R ²⁷ are 5 to 20 carbon atoms. The total carbon number of the four R ²⁷ is preferably 20 to 80, and more preferably 20 to 60.

The xanthracene dye (1) preferably contains any one or more of the compounds represented by the formulae (1-1) to (1-16). In formulas (1-1) to (1-16), Ra represents 2-ethylhexyl.

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

For example, the compounds represented by the formulae (1-1) to (1-8) and (1-15) can be produced by chlorinating a pigment or a pigment intermediate having -SO ₃ H by a general method. And reacting the obtained pigment or a pigment intermediate having -SO ₂ Cl with an amine represented by -NH ₂ R _a . In addition, it can also be produced by chlorinating a pigment produced by the method described in the upper right column to the lower left column of 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 the formulae (1-17) to (1-31).

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

As the xanthracene dye (1), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Sinochem Chemical Co., Ltd., Rhodamin) 6G "). Alternatively, a commercially available xanthracene dye may be used as a starting material and synthesized by referring to Japanese Patent Laid-Open No. 2010-32999.

Specific examples of the xanthracene dye (1) include CI Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. The same applies to others), 52, 87, 92, 94, 289, 388, etc. CI acid red dyes; CI acid violet dyes such as acid violet 9, 30, 102; CI basic red 1 (rhodamine 6G), 2, 3, 4, 8, 10, 11 and other CI basic red dyes; CI basic violet 10 (rhodamine B), 11, 25 and other CI basic violet dyes; CI solvent red (solvent red) 218 and other CI solvent red dyes; CI intermediate red (mordant red) 27 and other CI intermediate red dyes; CI reactive red (reactive red) 36 (rose bengal B) and other CI reactive red dyes; sulforhodamine (sulforhodamine) G; Japanese patent The xanthene dyes described in Japanese Patent Application Laid-Open No. 2010-32999; and the xanthene dyes described in Japanese Patent No. 4492760.

The total content ratio of CI Pigment Blue 15 in the colorant (A) to the red dye or purple dye, or the red dye and purple dye in the case where both are included (CI Pigment Blue 15 / red dye or purple dye, Or the red dye and the purple dye in the case where both of them are included) is usually 0.8 to 35 on a mass basis, and from the viewpoint of the tendency that x becomes lower and the brightness becomes higher, it is preferably 1 to 25, more preferably It is 1.1 to 20, and more preferably 1.2 to 15.

The colorant (A) may contain colorants other than CI Pigment Blue 15, a red dye, and / or a purple dye. Other colorants may be pigments (hereinafter, also referred to as other pigments), dyes (hereinafter, also referred to as other dyes), or both. Other colorants may be used alone or in combination of two or more. 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, known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye include a compound classified as a person having a hue other than pigment in the dye index (published by The Society of Dyers and Colourists), or a dyeing note (shikisensha company) Well-known dyes described in. In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, and azomethine dyes can be listed. Dyes, succinic acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, etc. Among these, an organic solvent-soluble dye is preferable.
The colorant (A) may contain other blue colorants (blue pigment and / or blue dye) than CI Pigment Blue 15. Examples of other blue pigments include CI Pigment Blue 15: 3, 15: 4, 15: 6, 16, 60, and the like.

Examples of blue dyes include:
CI 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 and other CI solvent blue dyes;
CI 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 and other CI acid blue dyes;
CI 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 and other CI direct blue dyes;
CI disperse blue (disperse blue) 1, 14, 56, 60 and other CI disperse blue dyes;
CI 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 and other CI basic blue dyes;
CI media 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 C.I. medium blue dyes;
Wait.

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

The content of CI Pigment Blue 15 in the colorant (A) is 100% by mass of the colorant (A), and is usually 20% to 99.9% by mass. From the viewpoint that x tends to decrease, it is preferably 40. Mass% to 95% by mass, and more preferably 50% to 90% by mass.
The content of the red dye or the purple dye in the colorant (A), or the red dye and the purple dye in the case of containing both of them, is 100% by mass of the colorant (A), usually 0.1% to 80% by mass. From the viewpoint that the brightness tends to increase, it is preferably from 5 to 60% by mass, and more preferably from 10 to 40% by mass.
When the colorant (A) contains an xanthracene dye as a red dye and a purple dye, the content of the xanthene dye in the colorant (A) is 100% by mass of the colorant (A), and preferably 0.1 mass % To 25% by mass, more preferably 0.5% to 20% by mass, and even more preferably 1% to 15% by mass. When the colorant (A) contains a xanthracene dye in the content in the above range, the brightness tends to be high.

The total content of the coloring agent (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. From the viewpoint that x of the xy chromaticity diagram tends to be low and brightness is higher, it is preferably 15% by mass or more, more preferably 20% by mass to 40% by mass, and even more preferably 25% by mass to 35% by mass. From the viewpoint of easily forming a resist pattern, the total content is preferably 45% by mass or less in 100% by 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 a moderate 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, "a solid content of a blue curable resin composition" means all components other than a solvent (E) among the components contained in a blue curable resin composition.

The various pigments used in the preparation of the blue curable resin composition are preferably in a state of a dispersion liquid uniformly dispersed in a solvent. The pigment preferably has a uniform particle size. The dispersion can be obtained by mixing a pigment with a solvent. If necessary, a pigment dispersant may be mixed. By including a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in a solvent can be obtained.
As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include silicone, fluorine, ester (including polyester), cationic, anionic, nonionic, amphoteric, polyester, and polyamine. Surfactants such as acrylic and acrylic. Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, In addition to tertiary amines modified polyurethanes, polyethyleneimines, etc., KP (Shin-Etsu Chemical Industry Co., Ltd.), Flolen (Kyoeisha Chemical Co., Ltd.) can also be listed as trade names. (Manufacturing), Solsperse (manufactured by Zeneca (stock)), EFKA (manufactured by BASF Japan (stock)), Ajisper (registered Trademark) (manufactured by Ajinomoto Fine-Techno), Disperbyk (by BYK-Chemie), etc. The pigment dispersant may be used alone or in combination of two or more.

When a pigment dispersant is used, its use amount is preferably 100 parts by mass or less with respect to 100 parts by mass of the pigment, and more preferably 5 to 50 parts by mass. When the usage-amount of a pigment dispersing agent exists in the said range, there exists a tendency for the pigment dispersion liquid of a uniform dispersion state to be easily obtained.

The solvent constituting the pigment dispersion liquid is not particularly limited, and examples thereof include the same solvents as those of the solvent (E) described later that can be contained in the blue curable resin composition. Among them, the solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethyl ether. Diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamidine Amines and the like are 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, and the like.

The use amount of the solvent is not particularly limited, and the concentration of the solid content in the pigment dispersion liquid is preferably an amount of 5 to 30% by mass, and more preferably 10 to 25% by mass.

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

〔2〕 Resin (B)
The blue curable resin composition of the present invention contains one kind or two or more kinds of resins (B). The resin (B) is preferably an alkali-soluble resin. The alkali-soluble property refers to a property of being dissolved in an aqueous solution of an alkali compound, that is, a developing solution. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) [hereinafter, sometimes referred to as "(a)"], and those having a carbon number of 2 to 4 Copolymer of a cyclic ether structure and an ethylenically unsaturated bond singular body (b) [hereinafter, sometimes referred to as "(b)"].
Resin [K2]: (a) and (b) and (a) and (a) copolymerizable monomer (c) (wherein it is different from (a) and (b)) [hereinafter, sometimes referred to as "(c) ”] Copolymer.
Resin [K3]: a copolymer of (a) and (c).
Resin [K4]: A resin obtained by reacting the copolymers of (b) and (a) with (c).
Resin [K5]: A resin obtained by reacting the copolymers of (a) and (b) with (c).
Resin [K6]: A resin obtained by reacting the copolymers of (a) and (b) with (c) and further reacting a carboxylic anhydride.

As (a), specifically:
Unsaturated monocarboxylic acids such as (meth) acrylic acid, butenoic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6- Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [ 2.2.1] Hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, and other bicyclic unsaturated compounds containing a carboxyl group;
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, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (5-norbornyl Unsaturated dicarboxylic anhydrides such as ene-2,3-dicarboxylic anhydride;
Mono (2- (meth) acrylfluorenyloxyethyl) succinate, mono- (2- (meth) acrylfluorenyloxyethyl) phthalate, and other polybasic carboxylic acids Unsaturated mono [(meth) acrylfluorenyloxyalkyl] ester;
Unsaturated (meth) acrylic acid containing α- (hydroxymethyl) (meth) acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule.
Among them, (a) is preferably (meth) acrylic acid, maleic anhydride, or the like from the viewpoint of copolymerization reactivity or the viewpoint of solubility in an alkaline aqueous solution.

In the present specification, the "(meth) acryl group" means at least one selected from the group consisting of an acrylic group and a methacryl group. The same applies to the expressions such as "(meth) acrylfluorenyl" 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 oxetane ring, an oxetane ring, and a tetrahydrofuran ring (oxetane ring) At least one) polymerizable compound with ethylenically unsaturated bonds. (B) It is preferable that it is a unit having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acrylfluorenyloxy group.
Examples of (b) include a singular body (b1) having an oxepropyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b1)"), and having an oxetanyl group and an ethylenic group. Unitary body (b2) of unsaturated bond (hereinafter, sometimes referred to as "(b2)"), unitary body (b3) with tetrahydrofuranyl group and ethylenically unsaturated bond [hereinafter, sometimes referred to as "(b3 )"〕Wait.

Examples of (b1) include a singular body (b1-1) [hereinafter, sometimes referred to as "(b1-1)"] having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon, and having an unsaturated lipid Unitary body (b1-2) [hereinafter, sometimes referred to as "(b1-2)"] having a structure obtained by epoxidizing a cyclic hydrocarbon.

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl group. 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 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, and the like.

Examples of (b1-2) include vinyl cyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Daicel) (Manufactured by Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl methyl (meth) acrylate (eg, Cyclomer A400; Daicel Chemical Industry Co., Ltd.), (Methyl) 3,4-epoxycyclohexyl methyl acrylate (for example, Cyclomer M100; Daicel Chemical Industry Co., Ltd.), a compound represented by formula (I), a compound represented by formula (II) Compounds etc.

[In formula (I) and formula (II), ^Raa and ^Rab independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X ^a1 and X ^a2 each independently represent a single ^{bond, * - R ac -, *} - R ac -O -, * - R ac -S-, or * -R ^ac -NH-; R ^ac represents 1 to 6 carbon atoms Alkyl diyl; * represents a bond with O]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, and third butyl.
Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group 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, and the like.
R ^aa and ^{Rab are} preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.
Examples of the alkanediyl group constituting R ^ac include methylene, ethylene, 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 X ^{a2 are} preferably a single bond, a methylene group, an ethylidene group, a * -CH ₂ -O- group (* represents a bond with O) group, a * -CH ₂ CH ₂ -O- group, and more It is preferably 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 preferred examples include formula (I-1) and formula (I-3). ), Formula (I-5), formula (I-7), formula (I-9), compounds represented by formula (I-11) to formula (I-15), more preferably, 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 preferred examples include formula (II-1) and formula (II-3). ), Formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), more preferably compounds of 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 at any ratio. In the case of mixing, the mixing ratio is based on formula (I): formula (II) [mole ratio], preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and further It is preferably 20:80 to 80:20.
The singlet (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a singlet having an oxetanyl group and a (meth) acrylfluorenyloxy group.
Preferred examples of (b2) include 3-methyl-3- (meth) acrylfluorenyloxymethyloxetane, and 3-ethyl-3- (meth) acrylfluorenyl Oxymethyloxetane, 3-methyl-3- (meth) propenyloxyethyloxetane, 3-ethyl-3- (meth) propenyloxy Ethyloxetane.
The singlet body (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is preferably a singlet body having a tetrahydrofuranyl group and a (meth) acrylfluorenyloxy group. Preferred examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and tetrahydrofurfuryl methacrylate.

Specific examples of (c) include:
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl ester, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) acrylate ring Hexyl ester, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester [method in this technical field is commonly used "Dicyclopentyl (meth) acrylate". It may also be referred to as "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decene-8-yl ester [methacrylic acid] Named "Dicyclopentenyl (meth) acrylate", Dicyclopentyloxyethyl (meth) acrylate, Isobornyl (meth) acrylate, Adamantane (meth) acrylate (Meth) acrylic acid, such as methyl ester, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. ester;
Hydroxy-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconic acid;
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, 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 -The third butoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] Hept-2-ene, 5,6-bis (third butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] heptane 2-ene and other bicyclic unsaturated compounds;
N-phenyl-cis-butene-diimide, N-cyclohexyl-cis-butene-diimide, N-benzyl-cis-butene-diimide, N-succinimide-imide-3-cis-butenedi Fluorenimide benzoate, N-succinimide imino-4-cis butylene diimide butyrate, N-succinimide imino-6-cis butene diimide hexanoate, N-succinimidylimide-3-cis-butene-diimide-propionate, N- (9-acridyl) -cis-butene-diimide-imide derivatives such as dicarbonylamide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, propylene Ammonium amine, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.
Among these, from the viewpoints of copolymerization reactivity and heat resistance, (c) is preferably benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylcis butylene difluorene Imines, N-cyclohexylcis-butenedifluoreneimine, N-benzylcis-butenedifluoreneimine, 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 and tricyclodecyl (meth) acrylate.

Of all the structural units constituting the resin [K1], the ratio of the structural units derived from each of the resin [K1] is preferably in the following range.
Structural unit derived from (a): 2 mol% to 50 mol% (more preferably 10 mol% to 45 mol%);
The structural unit derived from (b), especially the structural unit derived from (b1): 50 mol% to 98 mol% (more preferably 55 mol% to 90 mol%).
When the ratio of the structural unit of the resin [K1] is in the above range, there is a tendency that the storage stability, developability, and solvent resistance of the obtained pattern are excellent.
For the resin [K1], refer to the method described in the document "Experimental Methods for Polymer Synthesis" (by Otsu Takayuki, Chemical Dojin Publishing Co., Ltd., the first printing of the first edition, issued on March 1, 1972) and the Manufacturing is performed by citing documents described in the literature.
Specifically, a method of putting a predetermined amount of (a) and (b) (especially (b1)), a polymerization initiator, a solvent, and the like into a reaction vessel, and stirring, heating, and holding the heat in a deoxidizing environment can be mentioned. . In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, It can be used normally by users in this field. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or organic peroxides. (Benzamidine peroxide, etc.). As the solvent, any monomer may be used as long as it dissolves each monomer, and a solvent (E) and the like described later as the solvent of the blue curable resin composition can be used.
The obtained copolymer may be directly used as a solution after the reaction, a concentrated or diluted solution may be used, or it may be extracted as a solid (powder) by a method such as reprecipitation. In particular, during the polymerization, by using a solvent (E) described later as a solvent, the solution after the reaction can be used directly, and the production steps can be simplified.

Of all the structural units constituting the resin [K2], the ratio of the structural units derived from each resin in the resin [K2] is preferably in the following range.
Structural unit derived from (a): 4 mol% to 45 mol% (more preferably 10 mol% to 30 mol%);
Structural units derived from (b), especially structural units derived from (b1): 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% to 60 mol%).
When the ratio of the structural unit of the resin [K2] is within the above range, there is a tendency that the storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the obtained pattern are excellent.
The resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1]. Specifically, a predetermined amount of (a), (b) (especially (b1)), and (c), a polymerization initiator, and a solvent are charged into a reaction vessel, and the mixture is stirred, heated in a deoxidized environment, Method of insulation. The obtained copolymer may be directly used as a solution after the reaction, a concentrated or diluted solution may be used, or it may be extracted as a solid (powder) by a method such as reprecipitation.

Of all the structural units constituting the resin [K3], the ratio of the structural units derived from each of 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 method for producing the resin [K1].

The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and (b) a cyclic ether structure having 2 to 4 carbon atoms, in particular, an oxo ring having (b1) Propane cycloaddition is to the carboxylic acid and / or carboxylic anhydride which (a) has. Specifically, first, a copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each of all the structural units constituting the copolymer of (a) and (c) 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% to 90 mol%).

Next, the cyclic ether structure having 2 to 4 carbon atoms in (b), in particular, the oxetane ring in (b1) and the carboxylic acid and / or carboxylic acid derived from (a) in the copolymer Part of the acid anhydride is reacted. Specifically, after the production of the copolymer of (a) and (c), the environment in the flask was replaced with nitrogen from air, and (b) (especially (b1)), a carboxylic acid or carboxylic anhydride, and a cyclic ether Reaction catalysts (such as tris (dimethylaminomethyl) phenol) and polymerization inhibitors (such as hydroquinone) are added to the flask and reacted at 60 ° C to 130 ° C for 1 to 10 hours. With this, a resin [K4] can be obtained.
The used amount of (b), especially the used amount of (b1) is preferably 5 to 80 mol, and more preferably 10 to 75 mol, with respect to (a) 100 mol. By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable. In terms of high reactivity of the cyclic ether structure and difficulty in remaining unreacted (b), (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1) .
The use amount of the reaction catalyst is preferably 0.001% by mass to 5% by mass based on the total amount of (a), (b) (especially (b1)), and (c). The use amount of the polymerization inhibitor is preferably 0.001% by mass to 5% by mass based on the total amount of (a), (b), and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated during polymerization, and the like. In addition, in the same manner as the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated during polymerization, and the like.

Regarding the resin [K5], as the first step, a copolymer of (b) (especially (b1)) and (c) was obtained in the same manner as the method for producing the resin [K1]. In the same manner as described above, the obtained copolymer may be used directly after the reaction, a concentrated or diluted solution may be used, or it may be extracted using a method such as reprecipitation as a solid (powder).
The ratio of the structural units derived from (b) (especially (b1)) and (c) to the total mole number of all the structural units constituting the copolymer is preferably in the following range.
Structural units derived from (b), especially structural units derived from (b1): 5 mol% to 95 mol% (more preferably 10 mol% to 90 mol%);
Structural unit derived from (c): 5 mol% to 95 mol% (more preferably 10 mol% to 90 mol%).

Furthermore, under the same conditions as the method for producing the resin [K4], the copolymer of (a) and (b) (especially (b1)) and (c) has (b) derived from (b) ) The cyclic ether structure is reacted, whereby the resin [K5] can be obtained. The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mols relative to 100 mols in (b) (especially (b1)). In terms of high reactivity of the cyclic ether structure and difficulty in remaining unreacted (b), (b) used in the resin [K5] is preferably (b1), and more preferably (b1-1) .

Resin [K6] is a resin obtained by further reacting carboxylic anhydride and resin [K5]. The carboxylic acid anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether structure with a carboxylic acid or a carboxylic acid anhydride.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetraphthalic anhydride Hydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2- Ethylene anhydride (5-norbornene-2,3-dicarboxylic anhydride) and the like.

Among the resins [K1] to [K6], the preferred resin as the resin (B) is [K1] or [K2]. The resin (B) may include one resin or two or more resins.

The polystyrene equivalent weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000, and even more preferably 8,000 to 15,000. When the weight average molecular weight (Mw) is within the above-mentioned range, there is a tendency that the solubility of the unexposed portion in the developing solution is high, and the residual film rate or hardness of the obtained pattern is also high. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
The acid value of the resin (B) 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 to 150 mg-KOH / g, and more preferably 90 mg-KOH / g to 130 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by, for example, titration using an aqueous potassium hydroxide solution.
The content of the resin (B) is 100% by mass of the solid content of the blue curable resin composition, preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15% by mass. ～ 40% by mass. When content of resin (B) exists in the said range, there exists a tendency for the solubility of the unexposed part to the developing solution to become 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 living radicals generated from the polymerization initiator (D) due to light irradiation and the like, and examples thereof include polymerizable ethylenic unsaturated Bonded compounds, etc. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.
Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and examples thereof include trimethylolpropane tri (meth) acrylate and pentaerythritol tri (methyl) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol octa (meth) Acrylate, Tetrapentaerythritol Deca (meth) acrylate, Tetrapentaerythritol Nine (meth) acrylate, Tris (2- (meth) acrylfluorenyloxyethyl) isocyanurate, Glycol modification 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, hexane Lactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferred.
The blue curable resin composition of the present invention may contain one kind or two or more kinds of polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, and more preferably 50 to 120 parts by mass based on 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 capable of generating living radicals, acids, and the like by the action of light or heat to start polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include oxime-based compounds such as O-fluorenyl oxime compounds, benzoalkyl ketone compounds, biimidazole compounds, triazine compounds, and fluorenyl phosphine oxide compounds.
The polymerization initiator (D) may be used in combination of two or more in consideration of sensitivity and formation of a precise pattern shape. In terms of sensitivity and accurate correction of a pattern shape having a desired line width, the polymerization initiator (D) preferably contains an oxime-based compound such as an O-fluorenyl oxime compound.

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

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

[In formulas (d1) to (d3),
R ^d1 represents an aromatic hydrocarbon group having 6 to 18 carbons which may have a substituent, a heterocyclic group having 3 to 36 carbons which may have a substituent, an alkyl group having 1 to 15 carbons which may have a substituent, or an aromatic group A group having a substituent, which is a combination of a group hydrocarbon group and an alkanediyl group derived from the alkyl group, and the methylene group (-CH _2- ) contained in the alkyl group may be substituted with -O-, -CO -, -S-, -SO ₂ -or -NR ^d5- ;
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms;
R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbons which may have a substituent or a heterocyclic group having 3 to 36 carbons which may have a substituent;
R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, and the methylene group (-CH _2- ) may be substituted with -O -, - CO- or -S-, the aliphatic hydrocarbon group contained in the methine (-CH <) may be substituted with -PO ₃ <, the aliphatic hydrocarbon group as The hydrogen atom may be substituted by an OH group;
R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (-CH _2- ) contained in the alkyl group may be substituted with -O- or -CO-]

The carbon number of the aromatic hydrocarbon group represented by R ^d1 is preferably from 6 to 15, more preferably from 6 to 12, and even more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, preferably a phenyl group and a naphthyl group, and more preferably a phenyl group.
The aromatic hydrocarbon group represented by R ^d1 may have one or two or more substituents. The substituent is preferably substituted at the α or γ position of the aromatic hydrocarbon group, and more preferably substituted at the γ position.
Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecane 1-15 alkyl groups such as alkyl, tetradecyl and pentadecyl; halogen atoms such as fluorine atom, chlorine atom, iodine atom, bromine atom, etc.

The carbon number of the alkyl group as the substituent is preferably 1 to 10, and more preferably 1 to 7. The alkyl group as the substituent may be any of linear, branched, and cyclic groups, and may be a group obtained by combining 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-. The hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and is preferably substituted with a fluorine atom.
Examples of the alkyl group as a substituent in the aromatic hydrocarbon group represented by R ^d1 include a group represented by the following formula. In the formula, * represents a bond.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d1 include a group represented by the following formula. In the formula, * represents a bond.

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

[Wherein, R ^d6 represents an alkyl group having 1 to 10 carbon atoms which can be substituted with a halogen atom, and a hydrogen atom contained in R ^d6 may be substituted with a halogen atom; m2 represents an integer of 1 to 5; * represents a bonding bond ]

Examples of the alkyl group represented by R ^d6 include the same groups as those exemplified as the substituent of the aromatic hydrocarbon group represented by R ^d1 . The carbon number of R ^d6 is preferably 2 to 7, and more preferably 2 to 5. The alkyl group represented by R ^d6 may be any of linear, branched, and cyclic, and is preferably chain.
Examples of the halogen atom capable of replacing a 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 with a halogen atom, and more preferably 3 or more and 6 or less are substituted with a halogen atom. The substitution position of the R ^d6 O- group is preferably ortho and para, and particularly preferably para. m2 is preferably 1-2, and particularly preferably 1.
The carbon number of 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 pyrrolyl, furyl, thienyl, indolyl, benzofuryl, and carbazolyl.
The heterocyclic group represented by R ^d1 may have one or two or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent which 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. These alkyl groups may be any of linear, branched, and cyclic groups, and may be a group obtained by combining a chain group and a cyclic group. 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- , or a hydrogen atom may be used. 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, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear (straight or branched), cyclic, or any of linear, branched, and cyclic, and may be a chain and a ring A base formed by combining like bases. In the alkyl group of R ^d5 , methylene (-CH _2- ) may be substituted with -O- or -CO-.
Examples of the alkyl group which may have a substituent in R ^d1 include a group represented by the following formula. * Indicates a bond key.

Further, in R ^d1 , the number of carbon atoms of the group obtained by combining an aromatic hydrocarbon group and an alkanediyl group is preferably 7 to 33, more preferably 7 to 18, and even more preferably 7 to 12. The combination group may have one or two or more substituents, and examples of the substituent include the same groups as those exemplified as the aromatic hydrocarbon group and the substituent that the alkyl group may have. Examples of the group represented by this R ^{d1 in} which an aromatic hydrocarbon group and an alkanediyl group are combined include an aralkyl group, and specifically, a group represented by the following formula. In the formula, * represents a 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 from 6 to 15, more preferably from 6 to 12, and even more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a terphenyl group.
The carbon number of the heterocyclic group represented by R ^d2 is preferably from 3 to 20, more preferably from 3 to 10, even more preferably from 3 to 5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, and carbazolyl.
The carbon number of the alkyl group represented by R ^d2 is preferably 1 to 7, more preferably 1 to 5, and even 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 any of linear, branched, and cyclic groups, and may be a group obtained by combining 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, still more 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 ^{d 3} is preferably from 6 to 15, more preferably from 6 to 12, and even more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a terphenyl group. Preferred examples include a phenyl group and a naphthyl group.
The aromatic hydrocarbon group represented by R ^d3 may have one or two or more substituents. The substituent is preferably substituted at the α or γ position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and Alkyl groups having 1 to 15 carbons such as decyl; alkenyl groups having 1 to 15 carbons 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 carbon number of the aliphatic hydrocarbon group is more preferably from 1 to 7. The aliphatic hydrocarbon group may be any of linear, branched, and cyclic, and may 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 a group represented by the following formula. In the formula, * represents a bond.

Examples of the aromatic hydrocarbon group which may have a substituent in R ^d3 include a group represented by the following formula. In the formula, * represents a bond.

The carbon number of 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 pyrrolyl, furyl, thienyl, indolyl, benzofuryl, and carbazolyl. The heterocyclic group represented by R ^d3 may have one or two or more substituents, and examples of the substituent include the same groups as those exemplified as the substituent which the aromatic hydrocarbon group represented by R ^d1 may have.
Among them, R ^{d3 is} preferably an aromatic hydrocarbon group having a substituent. The substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms). Preferably it is 2 or more and 5 or less.

The carbon number of the aromatic hydrocarbon group represented by R ^d4 is preferably from 6 to 15, more preferably from 6 to 12, and even more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. A phenyl group and a naphthyl group are more preferable, and a phenyl group is more preferable. The aromatic hydrocarbon group represented by R ^d4 may have one or two or more substituents. Examples of the substituent include the same groups as those which 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 dodecane. Alkyl, 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-shaped (straight-chain or branched chain-shaped), may be cyclic, or may be a combination of a chain-shaped group and a cyclic group. In the aliphatic hydrocarbon group of R ^d4 , the methylene group (-CH _2- ) may be substituted with -O-, -CO- or -S-, and the methine group (-CH <) may be substituted with -PO ₃ <, The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
Examples of the aliphatic hydrocarbon group which may have a substituent represented by R ^d4 include a group represented by the following formula. In the formula, * represents a bond.

R ^{d4 is} preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and even more preferably a branched chain alkyl group having no substituent.

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

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[TABLE 6]

[TABLE 7]

Among them, compounds represented by formulas (d1-3) to (d1-6), compounds represented by formulas (d1-18) to (d1-52), and compounds represented by formula (d1-55) are preferred. A compound, a compound represented by formula (d1-56), a compound represented by formula (d1-60), a compound represented by formula (d1-61),
More preferred are compounds represented by formulas (d1-3) to (d1-6), compounds represented by formulas (d1-18) to (d1-41),
Furthermore, a compound represented by formula (d1-24), a compound represented by formula (d1-36) to formula (d1-40),
Particularly preferred is a compound represented by formula (d1-24).

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

The compound (d2) is preferably
R ^d1 is a C1-C15 alkyl group which may have a substituent,
R ^d2 is an alkyl group having 1 to 10 carbon atoms,
R ^d3 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent,
R ^d4 is a compound having an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent,
More preferably, R ^d1 represents methyl, ethyl or propyl, R ^d2 represents methyl, ethyl or propyl,
R ^d3 represents a methyl-substituted phenyl group,
Compounds where R ^d4 is methyl, ethyl or propyl,
Further preferred are compounds in which R ^d1 and R ^d2 are methyl groups, R ^d3 is o-tolyl group, and R ^d4 is ethyl group.
The compound (d3) is preferably
R ^d1 is a C1-C15 alkyl group which may have a substituent,
R ^d2 is an aromatic hydrocarbon group compound having 6 to 18 carbon atoms,
More preferred are compounds in which R ^d1 is a hexyl group and R ^d2 is a phenyl group.

Examples of such O-fluorenyl oxime compounds include N-benzyloxy-1- (4-phenylmercaptophenyl) butane-1-one-2-imine, and N-benzidine Phenyloxy-1- (4-phenylmercaptophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylmercaptophenyl) -3- Cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl ] Ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxa Cyclopentylmethyloxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxymethyl-1- [9-ethyl-6- ( 2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzylideneoxy-1- [9-ethyl-6 -(2-methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. You can also use commercially available products such as Irgacure OXE01, OXE02, and OXE03 (above, manufactured by BASF) and N-1919 (made by ADEKA). With these O-fluorenyl oxime compounds, there is a tendency that a blue color filter excellent in photolithography performance can be obtained.

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

Examples of the compound having a structure represented by the formula (d4) include 2-methyl-2-morpholinyl-1- (4-methylmercaptophenyl) propane-1-one and 2-dimethylamine. 1- (4-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- [4- (4-morpholinyl) phenyl] butane-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above, manufactured by BASF) can also be used.
Examples of the compound having a structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- ( 2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one Oligomers, α, α-diethoxyacetophenone, benzophenone dimethyl ketal, etc.
In terms of sensitivity, as the phenalkylone compound, a compound having a structure represented by formula (d4) is preferred.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-di (Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent 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. 48-38403, Japanese Patent Laid-Open) Sho 62-174204 and the like), imidazole compounds in which the 4,4 ', 5,5'-phenyl group is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Laid-Open No. 7-10913 and the like). Among them, a compound represented by the following formula or a mixture of these is preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, and 2,4-bis (trichloromethyl) ) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperidyl-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 Group] -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 fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine 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 benzophenybenzoate , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) diphenyl Benzophenone compounds such as ketone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2- Chloracridone, benzodiazone, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiator (D1) (especially an amine) described later.

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

[5] Polymerization initiation aid (D1)
The polymerization initiation aid (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound that is polymerized by a polymerization initiator. When a polymerization initiator (D1) is included, it can be used in combination with a polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thiaxanthone compounds, and carboxylic acid compounds. Among these, a xanthone compound is preferred. Two or more polymerization initiators (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 are preferably 4,4'-bis (diethylamino) benzophenone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the thioanthrone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. Anthrone, 1-chloro-4-propoxythioanthrone and the like.

Examples of the carboxylic acid compound include phenylmercaptoacetic acid, methylphenylmercaptoacetic acid, ethylphenylmercaptoacetic acid, methylethylphenylmercaptoacetic acid, dimethylphenylmercaptoacetic acid, and methoxyphenylmercapto Acetic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid , Naphthyloxyacetic acid, etc.

The content of the polymerization initiation aid (D1) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Serving. When the content of the polymerization initiator (D1) is within the above range, a blue pattern can be further formed with 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 contain one kind or two or more kinds of thiol compounds (T). The thiol compound (T) is particularly preferably used when the polymerization initiator (D) is an oxime-based compound such as an O-fluorenyl oxime compound and / or a biimidazole compound. The thiol compound (T) is a compound having at least one mercapto group (-SH) in the molecule. The thiol compound (T) is preferably a compound having one mercapto group in the molecule.

Examples of the compound having one mercapto group in the molecule include 2-mercaptooxazole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptofumes Basic acid, 2-mercaptopyridine, 2-mercaptopyridine-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-triazole, 3-amino-5-mercapto-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole Azole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-mercapto 1H-1,2,4-triazole-3-thiol, 2-amine Methyl-5-mercapto-1,3,4-thio Azole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dimercapto-1,3,4-thiadiazole, (furan-2-yl) methyl mercaptan, 2-mercapto-5-thiazolidinone, 2-mercaptothiazoline, 2-mercapto-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazol-5-thiol, 2-quinoline sulfur Alcohol, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 6-amino-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 6 -Ethoxy-2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercaptonaphthylimidazole, 2-mercaptonaphthoxazole, 3-mercapto-1,2,4-triazole Azole, 4-amino-6-mercaptopyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6-mercaptopurine, and 4-mercapto-1H-pyrazolo [2, 4-d] pyrimidine and the like.

Examples of the compound having two or more mercapto groups in the molecule include hexamethylene dithiol, sebacyl mercaptan, 1,4-bis (methylmercapto) benzene, butanediol bis (3-mercaptopropionate). , Butanediol bis (3-mercaptoacetate), ethylene glycol bis (3-mercaptoacetate), trimethylolpropane tri (3-mercaptoacetate), butanediol bis (3-mercaptoacetate) Propionate), trimethylolpropane tri (3-mercaptopropionate), trimethylolpropane tri (3-mercaptoacetate), pentaerythritol tetra (3-mercaptopropionate), pentaerythritol tetra (3 -Mercaptoacetate), trihydroxyethyltris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyloxy) butane, and the like.

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 parts by mass to 100 parts by mass of the polymerization initiator (D). 40 parts by mass. When content of a thiol compound (T) exists in the said range, there exists a tendency for sensitivity to become high and developability to become favorable.

[7] Solvent (E)
The blue curable resin composition of the present invention preferably contains one or two 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 (solvents containing -CO-) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene, and the like.

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, ethyl acetate, cyclamate Hexanol acetate and γ-butyrolactone.
Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, anisole, phenyl ether and methyl anisole.

Examples of the ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Diethyl 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 ethyl Acid esters and dipropylene glycol methyl ether acetate.

Examples of the ketone solvent 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.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene. Examples of the amidine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

In terms of coating properties and drying properties, the solvent (E) preferably contains an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm. Among them, the solvent (E) preferably contains a solvent 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-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, and N, N -At least one of the group consisting of dimethylformamide, more preferably 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.

The content of the solvent (E) in the blue curable resin composition is preferably 70% to 95% by mass, and more preferably 75% to 92% by mass. In other words, the solid content of the blue curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When content of a solvent (E) exists in the said range, the flatness at the time of coating will become favorable, and the color density will not become insufficient when a blue color filter is formed, and a display characteristic will become favorable.

〔8〕 Leveling agent (F)
The blue curable resin composition of the present invention may contain one or two or more leveling agents (F). Examples of the leveling agent (F) include a silicone-based surfactant (without a fluorine atom), a fluorine-based surfactant, and a silicone-based surfactant with a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specific examples include: 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 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 High-tech materials (manufactured by Momentive Performance Materials Japan).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), 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), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop ) EF352 (manufactured by Mitsubishi Materials Corporation), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass) (Stock) manufacturing) and E5844 (Daikin Fine Chemicals Research Institute (stock) manufacturing), etc.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant 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 (Dickson (DIC) (Shares) manufacturing) and so on.

The content of the leveling agent (F) in the blue curable resin composition is usually 0.001% by mass or more and 0.6% by mass or less, preferably 0.002% by mass or more and 0.4% by mass or less, and more preferably 0.005% by mass or more. And 0.2 mass% or less. Moreover, the 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 generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or the like can be used. The antioxidant may be used in two or more kinds.

Examples of the phenol-based antioxidant include Iranox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], BASF) (Manufacturing), Ilanox 1076 (Irganox 1076: octadecyl-3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate, BASF) (shares )), Ilanos 1330 (Irganox 1330: 3,3 ', 3' ', 5,5', 5 ''-Hexa-third-butyl-a, a ', a' '-(Junsan Toluene-2,4,6-triyl) tri-p-cresol, manufactured by BASF (stock), Elunox 3114 (Irganox 3114: 1,3,5-tris (3,5-di- Tertiary butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF 3790 (Irganox 3790: 1,3,5-tris ((4-third butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, manufactured by BASF (stock), Ilunox 1035 (Irganox 1035: thiodiethylenebis [3- (3,5-di-third 4-hydroxyphenyl) propionate], BASF (manufactured by BASF), Irganox 1135 (Irganox 1135: phenylpropionic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxyl, C7-C9 side chain alkyl ester, manufactured by BASF (stock), Elunox 1520L (Irganox 1520L: 4 , 6-Bis (octylthiomethyl) -o-cresol, manufactured by BASF (stock), Irganox 3125 (Irganox 3125, manufactured by BASF (stock)), Ilurus 565 ( Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-tert-butylaniline) -1,3,5-triazine, BASF (BASF ) (Manufactured), Adekastab AO-80 (Adekastab AO-80: 3,9-bis (2- (3- (3-third-butyl-4-hydroxy-5-methylphenyl) ) Propanyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, manufactured by ADEKA Corporation ), 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, Sumitomo Chemical (stock) manufacturing), Cynox 1790 (Cytec) (stock) and Vitamin E (Eisai (stock) manufacturing).

Examples of the phosphorus-based antioxidant include: Igrafos 168 (Igrafos 168: tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF) and Yilufos 12 (Igrafos 12: tris [2-[[2,4,8,10-tetra-third-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] Oxyoxy] ethyl] amine, manufactured by BASF (stock), Igrafos 38 (bis (2,4-bis (1,1-dimethylethyl) phosphite) -6- Methylphenyl) ethyl ester, manufactured by BASF (stock), Adekastab 329K (made by ADEKA), Adekastab PEP36 (Manufactured by ADEKA), Adekastab PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (Technology Made by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Utranox 626 (Ultranox 626, manufactured by GE), and Sumilizer GP, 6- [3- (3-Third-Butyl-4-hydroxyl -5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphaline (Manufactured by Sumitomo Chemical Co., Ltd.), etc.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and tetrakis. [Methylene (3-dodecylthio) propionate] A β-alkyl mercaptopropionate compound of a polyhydric alcohol such as methane.

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

[10] Other components The blue curable resin composition of the present invention may contain one or two or more fillers, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an anti-agglomerating agent, Additives such as organic acids, organic amine compounds, and hardeners.

Examples of the filler include glass, silicon dioxide, and alumina. Examples of the polymer compound other than the resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and N- (2-aminoethyl) -3. -Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-shrink Glyceryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

Examples of the ultraviolet absorber include benzotriazole compounds such as 2- (2-hydroxy-3-tertiarybutyl-5-methylphenyl) -5-chlorobenzotriazole; 2-hydroxy-4 -Benzophenone compounds such as octyloxybenzophenone; benzenes such as 2,4-di-third-butylphenyl-3,5-di-third-butyl-4-hydroxybenzoate Formate compounds; Triazine compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol; and the like. Examples of the anticoagulant include sodium polyacrylate.

Organic acids can be used to adjust the developability, and specifically include:
Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, hexanoic acid, diethylacetic acid, heptanoic acid, caprylic acid and other aliphatic monocarboxylic acids;
Glycolic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid , Ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid Aliphatic dicarboxylic acids such as acids, mesaconic acids;
Aliphatic tricarboxylic acids such as 1,2,3-tricarballylic acid, aconitic acid, and camphoronic acid;
Aromatic monocarboxylic acids such as benzoic acid, methyl benzoic acid, cumic acid, 2,3-xylolic acid, and 3,5-xylylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;
Aromatic polycarboxylic acids such as trimellitic acid, pyromellitic acid, mellophanic acid, pyromellitic acid, etc.

Examples of the organic amine compound include:
N-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, third butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine Monoalkylamines such as amines and n-dodecylamines;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-second butylamine, di-third Dialkylamines such as butylamine, di-n-pentylamine, and di-n-hexylamine;
Monoalkyl monocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicyclohexylamine and other bicycloalkylamines;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, three Trialkylamines such as isopropylamine, tri-n-butylamine, triisobutylamine, tri-second butylamine, tri-third butylamine, tri-n-pentylamine, and tri-n-hexylamine;
Dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, and tricyclohexylamine;
2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino Monoalkanolamines such as 1-hexanol;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Diethanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Bicycloalkanolamines such as bis (4-cyclohexanol) amine;
Triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine, and other trialkanolamines;
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-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1, 3-propanediol and other alkanediols;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol;
1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol and the like containing naphthene methanol;
1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylamino ring Hexane methanol, 4-diethylamino cyclohexane methanol, and other cycloalkane methanol containing amine groups;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5 -Amino carboxylic acids such as aminovaleric acid, 6-aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, p-n-propylaniline, p-isopropylaniline, p-n-butylaniline, p-thirdbutylaniline, 1-naphthalene Aromatic amines such as methylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
O-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol and other aminobenzyl alcohols;
O-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol and other aminophenols;
Aminobenzoic acid such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, and the like.

Examples of the curing agent include compounds that can react with the carboxyl group in the resin (B) to crosslink the resin (B) by heating, compounds that can be independently polymerized to harden the blue color filter, and the like. Oxygen compounds, oxetane compounds, and the like. The hardener may be used alone or in combination of two or more.

Examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, and others Epoxy resins such as aromatic epoxy resins, cycloaliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, and epoxy resins, or bromine of these epoxy resins Aliphatic, alicyclic or aromatic epoxy compounds other than alkylated derivatives, epoxy resins and brominated derivatives thereof, epoxy of (co) polymers of butadiene, (co) of isoprene ) Epoxides of polymers, (co) polymers of glycidyl (meth) acrylate, triglycidyl isocyanurate, and the like. Examples of commercially available epoxy resins include o-cresol novolac epoxy resin, "sumiepoxy (registered trademark) ESCN-195XL-80" (manufactured by Sumitomo Chemical Co., Ltd.), etc. .

Examples of the oxetane compound include dioxetane carbonate, xylylene dioxetane, adipic acid dioxetane, terephthalic acid dioxetane, Cyclohexanedicarboxylic acid dioxetane and the like.

When the blue curable resin composition of the present invention contains an epoxy compound, an oxetane compound, or the like as a hardener, the blue curable resin composition may include an epoxy group or an oxetane compound that can make the epoxy compound A compound in which an oxetane skeleton undergoes ring-opening polymerization. Examples of the compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators.

Examples of polycarboxylic acids include:
3,4-dimethylphthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ', 4,4'-benzophenone tetra Aromatic polycarboxylic acids such as carboxylic acids;
Aliphatic polycarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1, Alicyclic polycarboxylic acids such as 2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polycarboxylic acid anhydride include:
Aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride;
Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, 1,2,3-propanetricarboxylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride And other aliphatic polycarboxylic anhydrides;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclo Alicyclic polycarboxylic anhydrides such as pentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-norbornene-2,3-dicarboxylic anhydride, nadic anhydride;
Ester-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerol tritrimellitic anhydride.

As a carboxylic acid anhydride, you may use a commercial item as an epoxy resin hardener. Examples of the epoxy resin hardener include the product name "ADEKA Hardener (registered trademark) EH-700" (manufactured by ADEKA), and the product name "Richard ( Rikacid) (registered trademark) HH "(manufactured by Shin Nihon Chemical Co., Ltd.), trade name" MH-700 "(manufactured by Shin Nihon Chemical Co., Ltd.), etc.

Examples of the acid generator include 4-hydroxyphenyldimethylfluorene p-toluenesulfonate, 4-hydroxyphenyldimethylfluorene hexafluoroantimonate, and 4-ethoxyphenylphenyldimethylfluorene. P-Toluenesulfonate, 4-Ethyloxyphenyl · methyl · benzyl hexafluoroantimonate, triphenyl sulfonium p-toluenesulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyl Onium salts such as p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, or nitrobenzyltoluenesulfonate, benzoin tosylate, and the like.

<Manufacturing method of blue curable resin composition>
The blue curable resin composition of the present invention can be obtained by mixing a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and optionally a solvent (E) and sulfur. An alcohol compound (T), a leveling agent (F), a polymerization initiator (D1), an antioxidant (G), and other components are prepared by mixing.

<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 of a blue color filter. The blue color filter formed of the blue curable resin composition of the present invention also belongs to the scope of the invention of the present application. The blue color filter can also form a blue pattern.
Examples of the method for producing a blue pattern from the blue curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method, and a photolithography method is preferable. The photolithography method 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 photomask. In the photolithography method, a blue coating film as a cured product of the blue composition layer can be formed by not using a photomask during exposure and / or without performing development. The blue pattern or blue coating film formed from the blue curable resin composition of the present invention is a blue color filter of the present invention. The blue color filter of the present invention is typically used as a blue pixel.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass coated with silicon dioxide can be used; or polycarbonate, polymethyl methacrylate, poly Resin plates such as ethylene terephthalate; silicon; aluminum, silver, silver / copper / palladium alloy films, and the like are formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

The formation of each color pixel by the photolithography method can be performed under a known or customary device or condition, and can be produced, for example, as follows. First, a blue curable resin composition is coated on a substrate, and dried by heating (pre-baking) and / or drying under reduced pressure to remove a volatile component such as a solvent to obtain a smooth blue composition. Floor. Examples of the coating method include a spin coating method, a slit coating method, a slit and a spin coating method.

The temperature during heating and drying is preferably 30 ° C to 120 ° C, and more preferably 50 ° C to 110 ° C. The heating time is preferably 10 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. In the case of drying under reduced pressure, it is preferably carried out under a pressure of 50 Pa to 150 Pa in a temperature range of 20 ° C to 25 ° C. The film thickness of the blue composition layer is not particularly limited, and may be appropriately selected depending on 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 the 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 which generates light with a wavelength of 250 nm to 450 nm is preferable. For example, you can use a filter that cuts off this wavelength range for light less than 350 nm, or use a bandpass filter that extracts those wavelength ranges for light near 436 nm, 408 nm, and 365 nm. Perform selective extraction. Specifically, examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

During the exposure, in order to uniformly irradiate the entire exposed surface with parallel light, or to accurately position 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.

A blue pattern is formed on the substrate by developing the exposed blue composition layer by contacting the developing solution. By development, the unexposed part of the blue composition layer is dissolved in the developing solution and removed.
The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these basic compounds in the aqueous solution is preferably 0.01% by mass to 10% by mass, and more preferably 0.03% by mass to 5% by mass. Furthermore, the developing solution may contain a surfactant.

The development method may be any of a liquid coating method, a dipping method, and a spray method. Furthermore, the substrate can be tilted to an arbitrary angle during development. After development, washing with water is preferred.
Furthermore, it is preferable to post-bake the obtained blue pattern. The post-baking temperature is preferably 150 ° C to 250 ° C, and more preferably 160 ° C to 235 ° C. The post-baking time is preferably 1 minute to 120 minutes, and more preferably 10 minutes to 60 minutes.

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

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

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

Hereinafter, the present invention will be described more specifically by showing examples and comparative examples, but the present invention is not limited to these examples. In the examples,% and parts indicating content or used amount are mass standards unless otherwise specified.

<Synthesis Example 1: Pigment Dispersion Liquid (A1)>
CI Pigment Blue 15 12.1 parts of acrylic pigment dispersant 4.2 parts of propylene glycol monomethyl ether acetate 83.7 parts were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion liquid containing CI Pigment Blue 15 (A1 ).

<Synthesis Example 2: Pigment Dispersion Liquid (A2)>
CI Pigment Blue 15: 6 12.0 parts of acrylic pigment dispersant 2.0 parts of propylene glycol monomethyl ether acetate 86.0 parts were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment containing CI Pigment Blue 15: 6 Dispersion (A2).

<Synthesis Example 3: Pigment Dispersion Liquid (A3)>
CI Pigment Blue 15: 3 12.1 parts of acrylic pigment dispersant 3.6 parts of propylene glycol monomethyl ether acetate 84.3 parts were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment containing CI Pigment Blue 15: 3 Dispersion (A3).

<Synthesis Example 4: Pigment Dispersion Liquid (A4)>
CI Pigment Blue 15: 4 12.1 parts of acrylic pigment dispersant 3.6 parts of propylene glycol monomethyl ether acetate 84.3 parts were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment containing CI Pigment Blue 15: 4 Dispersion (A4).

<Synthesis Example 5: Pigment Dispersion Liquid (A5)>
CI Pigment Blue 16 12.1 parts of acrylic pigment dispersant 5.4 parts of propylene glycol monomethyl ether acetate 82.5 parts were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion liquid containing CI Pigment Blue 16 (A5 ).

<Synthesis Example 6: Pigment Dispersion Liquid (A6)>
CI Pigment Violet 23 12.0 parts of acrylic pigment dispersant 2.0 parts of propylene glycol monomethyl ether acetate 86.0 parts were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion liquid containing CI Pigment Violet 23 (A6 ).

<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 mixed liquid 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 was obtained as a residue by suction filtration, and then dried to obtain a compound represented by the formula (1-24). Hereinafter, this compound is referred to as an xanthracene dye (A7).

<Synthesis Example 8: Preparation of Resin (B)>
In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen was sufficiently flowed to set a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added. Heat to 70 ° C while stirring. Next, 60 parts of methacrylic acid and 240 parts of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate were dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution. The solution was added dropwise to the flask held at 70 ° C over 4 hours in a funnel.
On the other hand, using another dropping funnel for 4 hours, 30 parts of 2,2-azo (2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate. The mixed solution was added dropwise to the flask. After the dropwise addition was completed, the temperature was maintained at this temperature for 4 hours, and then the mixture was cooled to room temperature to obtain a resin solution having 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 a gel permeation chromatography (GPC) method under the following conditions. The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained under the following conditions was defined as the molecular weight distribution.

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

Device: HLC-8120GPC (manufactured by TOSOH)
Column: TSK-GELG2000HXL
Column temperature: 40 ℃
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Test solution solid content concentration: 0.001% by mass to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration reference material: TSK Standard Polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH)

<Examples 1 to 5 and Comparative Examples 1 to 5>
(1) Preparation of blue curable resin composition Each pigment dispersion liquid (A1) to pigment dispersion liquid (A6), xanthracene dye (A7), CI obtained in Synthesis Example 1 to Synthesis Example 6 Acid Red 52 (manufactured by Wako Pure Chemical Industries, Ltd.) (A8), CI Basic Violet 10 represented by the following formula (manufactured by Wako Pure Chemical Industries, Ltd., Rhodamine B) (A9), including the Resin solution of the resin (B) obtained in Synthesis Example 8, polymerizable compound (C), polymerization initiator (Da), polymerization initiator (Db), thiol compound (T), leveling agent (F ) It mixes so that it may become the compounding quantity shown in Table 8, and a blue curable resin composition is obtained.

When the blue curable resin composition was prepared, it was mixed with propylene glycol monomethyl ether acetate so that the color material concentration in the solid content of the blue curable resin composition was 30% by mass. The unit of the blending amount of each component in Table 8 is "mass parts", and the blending amount is converted into a solid content. The details of each component 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-dimethoxyphenyl) -4,5-diphenyl-1,1 '-Biimidazole (trade name "TCDM" manufactured by CHEMBRIDGE INTERNATIONAL CORPORATION),
Thiol compound (T): 2-mercaptobenzothiazole (trade name "Sanceler M" manufactured by Sanxin Chemical Industry Co., Ltd.),
Leveling agent (F): polyether modified silicone oil (trade name "Toray silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.).

[TABLE 8]

(2) Preparation of blue coating film On a 2-inch square glass substrate ("eagle XG" manufactured by Corning), a blue hardening resin composition was applied by spin coating. , Pre-bake at 100 ° C for 3 minutes. After cooling, the blue hardening was applied using an exposure machine ("TME-150RSK" manufactured by Topcon Corporation) at an exposure of 80 mJ / cm ² (365 nm basis) under atmospheric conditions. The substrate of the resin composition is irradiated with light. Then, it baked at 230 degreeC in the oven for 30 minutes, and obtained the blue coating film.

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

[TABLE 9]

In Examples 1 to 5 and Comparative Examples 1 to 5, y was unified to 0.095.
In Examples 1 to 5, compared with Comparative Example 1 showing the same x and y, high brightness can be obtained. In addition, in Comparative Example 2, although high brightness was obtained, compared with Examples 1 to 5, only high x was obtained.

no

no

Claims (5)

A blue curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and The colorant (A) includes C.I. Pigment Blue 15, and a red dye or a purple dye. The blue curable resin composition according to item 1 of the scope of patent application, wherein the red dye or purple dye contained in the colorant (A) is a compound having an xanthracene skeleton. The blue curable resin composition according to item 2 of the scope of patent application, wherein the content of the compound having a xanthracene skeleton is from 0.1% to 25% by mass in 100% by mass of the colorant (A). A blue color filter is formed of the blue curable resin composition according to any one of claims 1 to 3 of the scope of patent application. A display device includes the blue color filter described in item 4 of the scope of patent application.