KR102608327B1 - Blue curable resin composition, blue color filter, and display device comprising the same - Google Patents

Abstract

The object of the present invention is to provide a blue curable resin composition having a relatively low x of xy chromaticity in the is to provide.
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) includes CI Pigment Blue 15, a red dye, or a purple dye. Contains (red) dye.

Description

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

[0001] The present invention relates to a blue curable resin composition, a blue color filter, and a display device containing the same.

[0002] In recent years, demand for liquid crystal display devices with a wide displayable color reproduction area has been increasing.

In Patent Document 1, C.I. Pigment Blue 15 and C.I. A composition comprising a combination of Pigment Violet 23 has been proposed. In Patent Document 2, C.I. A composition comprising pigment blue 15:6 and a red dye has been proposed.

[0003] 1. Japanese Patent Publication No. 2005-316388 2. Japanese Patent Publication No. 2010-32999

[0004] The present invention provides a blue curable resin with a low x of the xy chromaticity diagram in the The object is to provide a composition, a blue color filter formed from the blue curable resin composition, and a display device including the blue color filter.

[0005] The present invention provides a blue curable resin composition, a blue color filter, and a display device shown below.

[0006] [1] It contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) is C.I. A blue curable resin composition containing Pigment Blue 15 and a red dye or a purple dye.

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

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

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

[5] A display device including the blue color filter described in [4].

[0007] According to the blue curable resin composition according to the present invention, it is possible to provide a blue color filter with low x of the xy chromaticity in the XYZ color system and high brightness, and a display device containing the same.

[0008] <Blue curable resin composition>

The blue curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) is C.I. It contains pigment blue 15 and a red dye or purple dye.

C.I. According to a blue curable resin composition containing a specific combination of Pigment Blue 15 and a red dye or a purple dye, it becomes possible to lower x of the xy chromaticity in the XYZ color system and increase brightness.

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

When y (hereinafter also referred to as y) of the xy chromaticity diagram in the

Brightness is the stimulus value (Y) in the XYZ color system, and the larger the value of Y, the higher the brightness tends to be.

The chromaticity coordinates and brightness of the xy chromaticity diagram in the

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

[0009] [1] Colorant (A)

In the blue curable resin composition according to the present invention, the colorant (A) is C.I. It contains pigment blue 15 and a red dye or purple dye. Since the blue curable resin composition contains a colorant (A), x of the xy chromaticity in the XYZ color system can be lowered and brightness can be increased, so it is useful as a material for a blue color filter.

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

[0010] Blue curable resin composition means that it has a maximum absorption wavelength of 580 nm to 650 nm.

[0011] As for the red dye and the purple dye, any one of them may be contained in the colorant (A), or both may be contained 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) is C.I. It may contain Pigment Blue 15 and red dye and/or purple dye.

[0012] The red dye refers to a dye having a maximum absorption wavelength of 480 to 560 nm, and the purple dye refers to a dye having a maximum absorption wavelength of 560 to 580 nm.

[0013] As the red dye and purple dye, one or two or more types of conventionally known red dyes and purple dyes can be used, respectively. From the viewpoint of the tendency for red dye and purple dye to increase brightness, it is preferable that they are compounds having a xanthene skeleton (hereinafter also referred to as “xanthene dye”).

[0014] The xanthene dye is preferably a compound represented by the following formula (1) (hereinafter also referred to as “xanthene dye (1)”). As for the xanthene dye (1), only 1 type may be used individually, and 2 or more types may be used together.

[0015]

[0016] [In formula (1), R ¹ to R ⁴ 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 each together form a ring containing a nitrogen atom. The hydrogen atom contained in the aromatic hydrocarbon group is 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 may be substituted. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ⁵ is -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 It represents ₂ NR ⁹ R ¹⁰ .

m represents an integer from 0 to 5. When m is an integer of 2 or more, a plurality of R ⁵ may be the same or different.

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

M ⁺ represents ⁺ 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, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and -CH contained in the saturated hydrocarbon group ₂ - may be substituted with -S-, -O-, -CO-, or -NR ¹¹ -. R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. When two or more R ^11s exist, all or part of them may be the same.

R ⁹ and R ¹⁰ independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with -OH or a halogen atom, or the saturated aliphatic group may be substituted with a halogen atom. -CH ₂ - contained in the hydrocarbon group may be substituted with -S-, -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ are bonded to each other and contain a nitrogen atom. It may form a 3- to 10-membered hetero ring. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.]

[0017] In R ¹ to R ⁴ in formula (1), examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group, and butylphenyl group. You can.

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

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

[0018]

[0019] For R ⁸ to R ¹¹ in formula (1), the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, and iso. Alkyl groups having 1 to 20 carbon atoms such as pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, and icosyl group; Cycloalkyl groups having 3 to 20 carbon atoms include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group.

[0020] With respect to the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ⁸ , the aromatic hydrocarbon group having 6 to 10 carbon atoms in which the hydrogen atom may be substituted includes phenyl group, toluyl group, xylyl group, mesityl group, and propylphenyl group. and butylphenyl group. In addition, 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 groups, * represents a bond.

[0021]

[0022]

[0023]

[0024]

[0025]

[0026] Examples of the alkyl group having 1 to 6 carbon atoms for R ⁶ and R ⁷ in formula (1) include those having 1 to 6 carbon atoms among the alkyl groups exemplified above.

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

[0027]

[0028] In the above formula, X ⁰ and X ² independently represent a halogen atom. Examples of the halogen atom for X ⁰ and X ² include a fluorine atom, a chlorine atom, and a bromine atom.

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035] Examples of the aralkyl group having 7 to 10 carbon atoms for R ¹¹ in formula (1) include benzyl group, phenylethyl group, and phenylbutyl group.

[0036] M ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and is preferably ⁺ N(R ¹¹ ) ₄ . ⁺ N(R ¹¹ ) ₄ It is preferable that among the four R ¹¹ , at least two are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Additionally, the total carbon number of four R ¹¹ is preferably 20 to 80, and more preferably 20 to 60.

[0037] The xanthene dye (1) is preferably a compound represented by formula (2).

[0038]

[0039] [In 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 is: It may be substituted with -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 represents 0 or 1.

m1 represents an integer from 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.

The four R ²⁷ independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.]

[0040] Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms for R ²¹ to R ²⁴ in formula (2) include the same groups as those exemplified as the aromatic hydrocarbon group for R ¹ to R ⁴ . can do. Among them, R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and when the hydrogen atom contained in the aromatic hydrocarbon group is substituted, the group to be substituted is -SO ₃ ^- , -SO ₃ ^{-M +} , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ are preferred. Furthermore, R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO ₃ ^{-M +} or -SO It is more preferable that it may be substituted with ₂ NHR ²⁶ . If R ²¹ to R ²⁴ are these groups, it is advantageous in forming a blue color filter with excellent heat resistance.

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

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

M ^a+ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and is preferably ⁺ N(R ²⁷ ) ₄ . ⁺ N(R ²⁷ ) ₄ is preferably a monovalent saturated hydrocarbon group with at least 2 of the 4 R ²⁷ groups having 5 to 20 carbon atoms. Moreover, the total carbon number of four R ²⁷ is preferably 20 to 80, and more preferably 20 to 60.

[0041] The xanthene dye (1) preferably contains one or more of the compounds represented by formulas (1-1) to (1-16). In addition, in formulas (1-1) to (1-16), Ra represents a 2-ethylhexyl group.

[0042]

[0043]

[0044]

[0045] Among these compounds, C.I. Sulfonamide of Acid Red 289 or C.I. The quaternary ammonium salt of Acid Red 289 is more preferred. Examples of such compounds include compounds represented by formulas (1-1) to (1-8), (1-11), and (1-12), respectively.

[0046] For example, the compounds represented by formulas (1-1) to (1-8) and formula (1-15) are obtained by chlorinating a dye or dye intermediate having -SO ₃ H according to a defined method. Thus, it can be produced by reacting the obtained dye or dye intermediate having -SO ₂ Cl with an amine represented by -NH ₂ R _a . In addition, the dye prepared by the method described in the upper right to lower left columns on page 3 of Japanese Patent Laid-Open Publication No. H03-78702 is chlorinated in the same manner as above, and then reacted with an amine. can do.

[0047] Another preferred xanthene dye (1) includes any one or more of the compounds represented by formulas (1-17) to (1-31).

[0048]

[0049]

[0050]

[0051] Compounds represented by formulas (1-17) to (1-31) can be produced according to the methods described in the upper right to lower left columns of page 3 of Japanese Patent Laid-Open No. H03-78702. . Examples of such methods include a method of reacting the compound represented by formula (1a), the compound represented by formula (1b), and the compound represented by formula (1c). In formula (1b) and formula (1c), R ¹ to R ⁴ each have the same meaning as above.

[0052]

[0053] The xanthene dye (1) is a commercially available xanthene dye (e.g., “Chugai Aminol Fast Pink R-H/C” manufactured by Chugai kasei Company, Limited, and “Rhodamin 6G” manufactured by Taoka Chemical Company, Limited). ) can be used. In addition, it can be synthesized using a commercially available xanthene dye as a starting material, with reference to Japanese Patent Laid-Open No. 2010-32999.

[0054] Specific examples of xanthene dye (1) include C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red will be omitted and only the number will be written. The same applies to the rest.), 52, 87, 92, 94, 289, 388, etc. Acid Red Dye; C.I. C.I. of Acid Violet 9, 30, 102, etc. Acid Violet Dye; C.I. C.I. such as Basic Red 1 (rhodamine 6G), 2, 3, 4, 8, 10, 11, etc. Basic Red Dye; C.I. C.I. of Basic Violet 10 (Rhodamine B), 11, 25, etc. Basic Violet Dye; C.I. C.I. such as Solvent Red 218. solvent red dye; C.I. C.I., including Mordant Red27. Mordant Red Dye; C.I. C.I. such as Reactive Red 36 (rose bengal B). Reactive Red Dye; sulforhodamine G; xanthene dye described in Japanese Patent Laid-Open No. 2010-32999; and xanthene dyes described in Japanese Patent Publication No. 4492760; etc. can be mentioned.

[0055] C.I. in colorant (A). Content ratio between Pigment Blue 15 and red dye or purple dye, or the sum of red dye and purple dye if both are included (C.I. Pigment Blue 15/red dye or purple dye, or both) When included, the amount (red dye and purple dye) is usually 0.8 to 35 on a mass basis, and from the viewpoint that x tends to decrease and brightness increases, it is preferably 1 to 25, more preferably 1.1. ~20, more preferably 1.2~15.

[0056] The colorant (A) is C.I. Pigment Blue 15 may contain colorants other than red dye and/or purple dye. The other colorant may be a pigment (hereinafter also referred to as another pigment), a dye (hereinafter also referred to as another dye), or all of these. As for other colorants, only one type may be used, or two or more types may be used in combination. Other pigments include organic pigments, inorganic pigments, and compounds classified as pigments in the Color 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. Dyes include compounds classified as having colors other than pigments in the Color Index (published by The Society of Dyers and Colourists), and those listed in the Dyeing Note (SHIKISENSHA CO., LTD. [色染社]) Known dyes may be mentioned. In addition, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, Squarylium dye, Cridine dye, styryl dye, coumarin dye, quinoline dye, nitro dye, etc. can be mentioned. Among these, organic solvent-soluble dyes are preferred.

The colorant (A) is C.I. Other blue colorants (blue pigments and/or blue dyes) other than Pigment Blue 15 may be included. As another blue pigment, C.I. Pigment blue 15:3, 15:4, 15:6, 16, 60, etc. can be exemplified.

[0057] As a blue dye,

C.I. 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, C.I. 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, etc. Solvent blue dye;

C.I. 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, 2 36, C.I. 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340, etc. Acid blue dye;

C.I. 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, 1 96, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 2 46, C.I. 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc. Direct blue dye;

C.I. C.I. such as Disperse Blue 1, 14, 56, 60, etc. Disperse Blue Dye;

C.I. 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, C.I. 67, 68, 81, 83, 88, 89, etc. Basic Blue Dye;

C.I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84, etc. C.I. Mordant blue dye;

etc. can be mentioned.

[0058] However, from the viewpoint of lowering x and improving brightness, C.I. in the colorant (A). When Pigment Blue 15, red dye or purple dye, or both are included, the greater the total content of red dye and purple dye, the more preferable it is. Specifically, C.I. in the colorant (A). When Pigment Blue 15, red dye or purple dye, or both are included, the total content of red dye and purple dye is preferably 50 to 100% by mass in 100% by mass of colorant (A), More preferably, it is 70 to 100 mass%, still more preferably 80 to 100 mass%, and particularly preferably 90 to 100 mass%.

[0059] C.I. in the colorant (A). The content of Pigment Blue 15 is usually 20 to 99.9% by mass in 100% by mass of colorant (A), and from the viewpoint that x tends to be low, it is preferably 40 to 95% by mass, more preferably 50% by mass. It is ~90% by mass.

When the colorant (A) contains red dye or purple dye, or both, the content of the red dye and purple dye is usually 0.1 to 80% by mass in 100% by mass of the colorant (A), and the content of the colorant (A) increases. From the viewpoint of tendency, it is preferably 5 to 60 mass%, more preferably 10 to 40 mass%.

When the colorant (A) contains a xanthene dye as a red dye and a purple dye, the content of the xanthene dye in the colorant (A) is preferably 0.1 to 25% by mass, based on 100% by mass of the colorant (A). Preferably it is 0.5 to 20 mass %, more preferably 1 to 15 mass %.

When the colorant (A) contains xanthene dye in a content within the above range, brightness tends to increase.

[0060] The total content of the colorant (A) in the blue curable resin composition is usually 10 to 50% by mass based on 100% by mass of solid content of the blue curable resin composition, but x of the xy chromaticity diagram in the XYZ colorimetric system is low. From the viewpoint that the brightness tends to increase, it is preferably 15% by mass or more, more preferably 20 to 40% by mass, and even more preferably 25 to 35% by mass. From the viewpoint of ease of forming a resist pattern, the total content is preferably 45% by mass or less in 100% by mass of solid content of the blue curable resin composition.

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

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

[0061] The various pigments used in the preparation of the blue curable resin composition are preferably in a dispersion state uniformly dispersed in a solvent. Additionally, the pigment preferably has a uniform particle size. The dispersion liquid can be obtained by mixing a pigment and a solvent. If necessary, a pigment dispersant may be mixed. By containing a pigment dispersant and performing dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in the solvent can be obtained.

As a pigment dispersant, commercially available surfactants can be used, including silicone-based, fluorine-based, ester-based (including polyester-based), cationic, anionic, nonionic, amphoteric, polyamine-based, and acrylic-based. Surfactants may be mentioned. Specific examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. In addition, product names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by KYOEISHA CHEMICAL Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), and EFKA (manufactured by BASF JAPAN LTD.) , Ajispa (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Inc.), and Disperbyk (manufactured by BYK-Chemie). As for the pigment dispersant, only one type may be used, or two or more types may be used together.

[0062] When using a pigment dispersant, the amount used is preferably 100 parts by mass or less, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the pigment. If the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be easily obtained.

[0063] The solvent constituting the pigment dispersion is not particularly limited and includes solvents such as the solvent (E) described later that may be contained in the blue curable resin composition. Among them, the solvent is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3 -Methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc. are preferred, and propylene glycol monomethyl ether acetate and propylene glycol. Monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxy ethyl propionate, etc. are preferable.

[0064] The amount of solvent used is not particularly limited, but is an amount such that the concentration of solid content in the pigment dispersion is preferably 5 to 30% by mass, more preferably 10 to 25% by mass.

[0065] The various pigments used in the preparation of the blue curable resin composition are, if necessary, surface treated using rosin treatment, pigment derivatives into which acidic or basic groups are introduced, pigment dispersants, etc. , grafting treatment on the surface of the pigment with a polymer compound, etc., atomization treatment using a sulfuric acid atomization method, etc., or washing treatment with an organic solvent or water to remove impurities, or removal treatment using an ion exchange method for ionic impurities. etc. may be implemented.

[0066] [2] Resin (B)

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

[0067] Resin [K1]: At least one (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a carbon number of 2 to 2. A copolymer of monomer (b) (hereinafter sometimes referred to as “(b)”) having a tetracyclic ether structure and an ethylenically unsaturated bond.

Resin [K2]: (a) and (b), and monomer (c) copolymerizable with (a) (however, it is different from (a) and (b).) [hereinafter referred to as “(c)” Copolymer of].

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

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

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

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

[0068] As (a), specifically,

Unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 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- Bicyclo unsaturated compounds containing a carboxyl group such as methylbicyclo[2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic acid anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (himic acid anhydride);

Unsaturated mono[(meth)acryloyloxyalkyl of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, etc. 〕ester;

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

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

[0069] In this specification, “(meth)acrylic” refers to at least one type selected from the group consisting of acrylic and methacryl. The same applies to expressions such as “(meth)acryloyl” and “(meth)acrylate.”

[0070] (b) is a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and an ethylenic ring. It refers to a polymerizable compound that has an unsaturated bond. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

As (b), monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as “(b1)”], monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter. , sometimes referred to as “(b2)”], monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as “(b3)”], etc.

[0071] As (b1), monomer (b1-1) (hereinafter sometimes referred to as “(b1-1)”) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon, unsaturated alicyclic type. and monomer (b1-2) (hereinafter sometimes referred to as “(b1-2)”) having a structure obtained by epoxidizing a hydrocarbon.

[0072] As (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o -Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl Ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene Cydyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl) ) Styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene etc. can be mentioned.

[0073] Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy4-vinylcyclohexane (e.g., Seroxide 2000; manufactured by Daicel Chemical Industries, Ltd.), and 3,4-epoxycyclohexylmethyl. (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), A compound represented by formula (I), a compound represented by formula (II), etc. can be mentioned.

[0074]

[0075] [In Formula (I) and Formula (II), R ^aa and R ^ab each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. It may be substituted. X ^a1 and X ^a2 independently of each other represent a single bond, *-R ^ac -, *-R ^ac -O-, *-R ^ac -S-, or *-R ^ac -NH-. R ^ac represents an alkanediyl group having 1 to 6 carbon atoms. * indicates a bond with O.]

[0076] Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group.

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

R ^aa and R ^ab 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.

Alkanediyl groups constituting R ^ac include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. diyl group, hexane-1,6-diyl group, etc.

_[ ⁰⁰⁷⁷ _{] X} ^a1 and It is a group, more 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), preferably formula (I-1) and formula (I-3). ), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), and more preferably compounds represented by formula (I-15). Compounds represented by (I-1), formula (I-7), formula (I-9), and formula (I-15) can be mentioned.

[0078]

[0079]

[0080] Specific examples of the compound represented by formula (II) include compounds represented by formula (II-1) to formula (II-15), preferably formula (II-1) and formula (II) -3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), and more preferably, Examples include compounds represented by formula (II-1), formula (II-7), formula (II-9), and formula (II-15).

[0081]

[0082]

[0083] The compound represented by formula (I) and the compound represented by formula (II) can each be used individually. These can be mixed in any ratio. When mixing, the mixing ratio is Formula (I):Formula (II) [molar ratio], preferably 5:95 to 95:5, more preferably 10:90 to 90:10, even more preferably 20：80~80：20.

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

Preferred examples of (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth) ) Acryloyloxyethyloxetane and 3-ethyl-3-(meth)acryloyloxyethyloxetane.

The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group.

Preferred examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscot V#150, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD), tetrahydrofurfuryl methacrylate, and the like.

[0084] As a specific example of (c),

Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate Rate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate [in the relevant technical field, it is called “dicyclofentanyl (meth)acrylate” as a common name. It is also sometimes called “tricyclodecyl (meth)acrylate”], tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate [in the relevant technical field, as a common name “ It is called “dicyclopentenyl (meth)acrylate”, dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate. (meth)acrylic acid esters such as propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

(meth)acrylic acid esters containing hydroxy groups, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -N, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-Butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoc Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyl oxide Bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- Dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid. Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

can be mentioned.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, examples of (c) include benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N- Benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferred. In addition, benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable as (c) because of their excellent developability during pattern formation.

[0085] In the resin [K1], the ratio of structural units derived from each is preferably within the following range among all structural units constituting the resin [K1].

Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol%),

Structural units derived from (b), especially structural units derived from (b1); 50 to 98 mol% (more preferably 55 to 90 mol%).

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

Resin [K1] was prepared by the method described in the literature “Experimental Methods for Polymer Synthesis” (written by Takayuki Otsu, published by Kagaku-Dojin Publishing Company, INC., 1st edition, 1st printing, published March 1, 1972) and the literature. It can be prepared by referring to the cited literature.

Specifically, a method of charging a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent, etc. into a reaction vessel and stirring, heating, and keeping warm in a deoxygenated atmosphere is given. You can. In addition, the polymerization initiator and solvent used here are not particularly limited, and any of those commonly used in the relevant field can be used. Polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). there is. The solvent may be any solvent that dissolves each monomer, and solvents such as solvent (E) described later can be used as a solvent for the blue curable resin composition.

The obtained copolymer may be used as is, as a solution after the reaction, as a concentrated or diluted solution, or as a solid (powder) extracted by a method such as re-precipitation. In particular, by using the solvent (E) described later as the solvent during this polymerization, the solution after the reaction can be used as is, and the manufacturing process can be simplified.

[0086] In the resin [K2], the ratio of structural units derived from each is preferably within the following range among all structural units constituting the resin [K2].

Structural unit derived from (a); 4 to 45 mol% (more preferably 10 to 30 mol%),

Structural units derived from (b), especially structural units derived from (b1); 2 to 95 mol% (more preferably 5 to 80 mol%),

Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%).

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

Resin [K2] can be produced in the same manner as the method described as the production method for resin [K1]. Specifically, a method of charging a predetermined amount of (a), (b) (particularly (b1)), and (c), a polymerization initiator, and a solvent into a reaction vessel, followed by stirring, heating, and keeping warm in a deoxygenated atmosphere. You can. The obtained copolymer may be used as a solution after the reaction, a concentrated or diluted solution, or one extracted as a solid (powder) by a method such as reprecipitation.

[0087] In resin [K3], the ratio of structural units derived from each is preferably within the following range among all structural units constituting resin [K3].

Structural unit derived from (a); 2 to 55 mol% (more preferably 10 to 50 mol%),

Structural unit derived from (c); 45 to 98 mol% (more preferably 50 to 90 mol%).

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

[0088] Resin [K4] is obtained by obtaining a copolymer of (a) and (c), and the cyclic ether structure having 2 to 4 carbon atoms of (b), especially the oxirane ring of (b1), is added to (a) It can be prepared by adding it to a branched carboxylic acid and/or carboxylic acid anhydride. Specifically, first, the copolymers (a) and (c) are produced in the same manner as the method described as the production method for resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all structural units constituting the copolymers (a) and (c).

Structural unit derived from (a); 5 to 50 mol% (more preferably 10 to 45 mol%),

Structural unit derived from (c); 50 to 95 mol% (more preferably 55 to 90 mol%).

[0089] Next, a portion of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the above copolymer has a cyclic ether structure having 2 to 4 carbon atoms of (b), especially (b1). The branch reacts the oxirane ring. Specifically, following the production of the copolymers of (a) and (c), the atmosphere in the flask is changed from nitrogen to air, and (b) (particularly (b1)) is mixed with a carboxylic acid or carboxylic anhydride and a ring. A reaction catalyst with a shaped ether structure (such as tris(dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (such as hydroquinone) are placed in a flask and reacted at 60 to 130° C. for 1 to 10 hours to form a resin [ K4] can be obtained.

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

The amount of the reaction catalyst used is preferably 0.001 to 5% by mass relative to the total amount of (a), (b) (particularly (b1)), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass based on the total amount of (a), (b), and (c).

Reaction conditions such as input method, reaction temperature and time can be adjusted appropriately taking into account the manufacturing equipment and the amount of heat generated by polymerization. In addition, as with the polymerization conditions, the charging method and reaction temperature can be adjusted appropriately by taking into consideration the manufacturing equipment, the amount of heat generated by polymerization, etc.

[0090] In the first step, resin [K5] is prepared in the same manner as the above-described method for producing resin [K1] to obtain a copolymer of (b) (particularly (b1)) and (c). Similarly to the above, the obtained copolymer may be used as a solution after the reaction, a concentrated or diluted solution, or extracted as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) (particularly (b1)) and (c) is preferably within the following range with respect to the total number of moles of all structural units constituting the above copolymer.

Structural units derived from (b), especially structural units derived from (b1); 5 to 95 mol% (more preferably 10 to 90 mol%),

Structural unit derived from (c); 5 to 95 mol% (more preferably 10 to 90 mol%).

[0091] In addition, under the same conditions as the production method of resin [K4], the cyclic ether structure derived from (b) of the copolymer of (b) (particularly (b1)) and (c), (a) Resin [K5] can be obtained by reacting carboxylic acid or carboxylic acid anhydride. The amount of (a) used to react with the above copolymer is preferably 5 to 80 moles per 100 moles of (b) (particularly (b1)). Since the reactivity of the cyclic ether structure is high and it is difficult for unreacted (b) to remain, (b1) is preferred as (b) used in resin [K5], and (b1-1) is more preferred.

[0092] Resin [K6] is a resin obtained by reacting resin [K5] with a carboxylic acid anhydride.

A carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction between the cyclic ether structure and the carboxylic acid or carboxylic acid anhydride.

As carboxylic acid anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3, Examples include 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride).

[0093] Among the resins [K1] to [K6], the resin preferred as the resin (B) is [K1] or [K2]. Resin (B) may consist of one type of resin or may contain two or more types of resin.

[0094] The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 5,000 to 30,000, and even more preferably The average is 8,000 to 15,000. When the weight average molecular weight (Mw) is within the above range, the solubility of the unexposed portion in the developer is high, and the residual film rate and hardness of the resulting pattern also tend to be 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 to 200 mg-KOH/g, more preferably 50 to 180 mg-KOH/g, and even more preferably 80 to 150 mg-KOH. /g, and even more preferably 90 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 resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

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

[0095] [3] Polymerizable compound (C)

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) by irradiation of light, etc., and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. . 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, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythate. Litol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate Late, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra( Meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified penta Erythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc. are mentioned. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferable.

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

[0096] [4] Polymerization initiator (D)

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

[0097] Examples of the polymerization initiator (D) include oxime compounds such as O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

Two or more types of polymerization initiators (D) may be used in combination, taking into account sensitivity, ability to form precise pattern shapes, etc. The polymerization initiator (D) preferably contains an oxime-based compound such as an O-acyloxime compound because it is advantageous in precisely creating a pattern shape with sensitivity and desired line width.

[0098] An O-acyloxime compound is a compound having a structure represented by formula (d). Hereinafter, * represents a bond.

[0099]

[0100] O-acyloxime compounds include compounds represented by formula (d1) (hereinafter sometimes referred to as “compound (d1)”), compounds represented by formula (d2) (hereinafter referred to as “compound (d2)” )”), and a compound represented by formula (d3) (hereinafter sometimes referred to as “compound (d3)”). It is preferable that it is at least one type selected from the group consisting of.

[0101]

[0102] [In equations (d1) to (d3),

R ^d1 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or an aromatic hydrocarbon group and the corresponding alkyl group. It represents a group that may have a substituent combining an alkanediyl group derived from, and the methylene group (-CH ₂ -) contained in the alkyl group is -O-, -CO-, -S-, - It may be substituted with 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 carbon atoms which may have a substituent, or a heterocyclic group having 3 to 36 carbon atoms 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 -) contained in the aliphatic hydrocarbon group is - It may be substituted with O-, -CO-, or -S-, and the methine group (-CH<) contained in the aliphatic hydrocarbon group may be substituted with -PO ₃ <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be It may be substituted with 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-.]

[0103] The carbon number of the aromatic hydrocarbon group represented by R ^d1 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, terphenyl group, etc., preferably phenyl group and naphthyl group, more preferably phenyl group. there is.

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

Examples of the substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc. an alkyl group having 1 to 15 carbon atoms; Halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; etc. can be mentioned.

[0104] 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 straight chain, branched, and cyclic groups, and may be a combination of a chain group and a ring group. The methylene group (-CH ₂ -) contained in the alkyl group as the substituent may be substituted with -O- or -S-. Additionally, 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, or a bromine atom, and is preferably substituted with a fluorine atom.

In the aromatic hydrocarbon group represented by R ^d1 , examples of the alkyl group as a substituent include groups represented by the formula below. In the formula, * represents a binding hand.

[0105]

[0106]

[0107] Examples of the aromatic hydrocarbon group that may have a substituent represented by R ^d1 include groups represented by the formula below. In the formula, * represents a binding hand.

[0108]

[0109]

[0110] For R ^d1 , the aromatic hydrocarbon group that may have a substituent is preferably a group represented by the formula below.

[0111]

[0112] [In the formula, R ^d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and the hydrogen atom contained in R ^d6 may be substituted with a halogen atom. m2 represents an integer of 1 to 5. * indicates a bonding hand.]

[0113] Examples of the alkyl group represented by R ^d6 include the same groups as the alkyl groups exemplified as substituents of the aromatic hydrocarbon group represented by R ^d1 . The number of carbon atoms of R ^d6 is preferably 2 to 7, and more preferably 2 to 5. Additionally, the alkyl group represented by R ^d6 may be linear, branched, or ring-shaped, and is preferably chain-shaped.

Examples of the halogen atom that may be replacing the hydrogen atom contained in R ^d6 include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and a fluorine atom is particularly preferable. It is preferable that 2 or more and 10 or less of the hydrogen atoms contained in R ^d6 are substituted with halogen atoms, and it is more preferable that 3 or more and 6 or less hydrogen atoms are substituted with halogen atoms. The position of substitution of the R ^d6 O- group is preferably the ortho position or the para position, and the para position is particularly preferable. It is preferable that m2 is 1-2, and it is especially preferable that it is 1.

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

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 substituents that the aromatic hydrocarbon group represented by R ^d1 may have.

The number of carbon atoms of the alkyl group represented by R ^d1 is preferably 1 to 12. The alkyl group represented by R ^d1 includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, and Pentadecyl group, etc. can be mentioned. These alkyl groups may be straight chain, branched, or cyclic, and may be a combination of a chain group and a cyclic group. In addition, in the alkyl group represented by R ^d1 , the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 -, and may be substituted with a hydrogen atom. may be substituted with an 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 chain-shaped (straight-chain or branched) or cyclic, or may be any of straight-chain, branched, and cyclic, or may be a combination of a chain-shaped group and a cyclic group. In the alkyl group of R ^d5 , the methylene group (-CH ₂ -) may be substituted with -O- or -CO-.

For R ^d1 , specific examples of the alkyl group that may have a substituent include groups represented by the following formula. * represents the bonding hand.

[0114]

[0115] Furthermore, in R ^d1 , the carbon number of the group combining an aromatic hydrocarbon group and an alkanediyl group is preferably 7 to 33, more preferably 7 to 18, and still more preferably 7 to 12. The combined group may have one or two or more substituents, and examples of the substituent include the same groups as those exemplified as the substituents that an aromatic hydrocarbon group and an alkyl group may have. Examples of the group represented by R ^d1 in combination with an aromatic hydrocarbon group and an alkanediyl group include an aralkyl group, and specifically, a group represented by the following formula. In the formula, * represents a binding hand.

[0116]

[0117] Among them, R ^d1 is preferably an aromatic hydrocarbon group that may have a substituent or an alkyl group that may have a substituent, and more preferably an aromatic hydrocarbon group that may have a substituent.

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

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

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

R ^d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, even 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 ^d3 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, and terphenyl group, and preferably phenyl group and 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-position or γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, and specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups having 1 to 1 carbon atoms. ~15 alkyl group; Alkenyl groups having 1 to 15 carbon atoms such as ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, nonenyl group, and decenyl group; etc. can be mentioned.

The aromatic hydrocarbon group represented by R ^d3 may have an aliphatic hydrocarbon group. It is more preferable that the carbon number of the aliphatic hydrocarbon group is 1 to 7, and the aliphatic hydrocarbon group may be any of straight chain, branched, and cyclic, or may be a combination of a chain and a cyclic group. 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<. You can stay.

Examples of the aliphatic hydrocarbon group include groups represented by the following formula. In the formula, * represents a binding hand.

[0118]

[0119] For R ^d3 , examples of aromatic hydrocarbon groups that may have substituents include groups represented by the formula below. In the formula, * represents a binding hand.

[0120]

[0121] The carbon number of the heterocyclic group represented by R ^d3 is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include pyrrolyl group, furyl group, thienyl group, indolyl group, benzofuryl group, and carbazolyl group. 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 substituents that the aromatic hydrocarbon group represented by R ^d1 may have.

Among them, R ^d3 is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms), and the number of substituents is 2 or more. , it is desirable to have 5 or less.

[0122] The carbon number of the aromatic hydrocarbon group represented by R ^d4 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, and terphenyl group, with phenyl group and naphthyl group being more preferable, and phenyl group being still more preferable. Additionally, the aromatic hydrocarbon group represented by R ^d4 may have one or two or more substituents. Examples of the substituent include the same group as the substituent that the aromatic hydrocarbon group of R ^d1 may have.

The carbon number of the aliphatic hydrocarbon group represented by R ^d4 is preferably 1 to 13, more preferably 2 to 10, and still more preferably 4 to 9. The aliphatic hydrocarbon group represented by R ^d4 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl. Alkyl groups such as syl group and pentadecyl group; Alkenes such as ethene group, propene group, butene group, pentene group, hexenyl group, heptenyl group, octenyl group, nonene group, decene group, undecene group, dodecene group, tridecene group, butadecenyl group and pentadecenyl group. Nil group; etc. can be mentioned. These aliphatic hydrocarbon groups may be chain-shaped (straight-chain or branched), ring-shaped, or a combination of a chain-shaped group and a ring-shaped 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 <. Alternatively, the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.

Examples of the aliphatic hydrocarbon group that may have a substituent represented by R ^d4 include groups represented by the formula below. In the formula, * represents a binding hand.

[0123]

[0124] R ^d4 is preferably a chain aliphatic hydrocarbon group that may have a substituent, more preferably a chain alkyl group without a substituent, and even more preferably a branched alkyl group without a substituent.

[0125] Compound (d1) includes compounds represented by formula (d1), specifically compounds (d1-1) to (d1-67) having each substituent shown in Tables 1 to 7. In Tables 1 to 7, * indicates a bonding hand.

[0126]

[0127] [Table 1]

[0128] [Table 2]

[0129] [Table 3]

[0130] [Table 4]

[0131] [Table 5]

[0132] [Table 6]

[0133] [Table 7]

[0134] Among them, compounds represented by formulas (d1-3) to (d1-6), compounds represented by formulas (d1-18) to formulas (d1-52), and compounds represented by formulas (d1-55) A compound represented by the formula (d1-56), a compound represented by the formula (d1-60), and a compound represented by the formula (d1-61) are preferred,

Compounds represented by formulas (d1-3) to (d1-6) and compounds represented by formulas (d1-18) to (d1-41) are more preferable,

Compounds represented by formula (d1-24) and compounds represented by formulas (d1-36) to (d1-40) are more preferable,

Compounds represented by formula (d1-24) are particularly preferred.

[0135] Compound (d1) can be produced, for example, by the production method described in Japanese Patent Publication No. 2014-500852.

[0136] As compound (d2),

R ^d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent,

R ^d2 is an alkyl group having 1 to 10 carbon atoms,

R ^d3 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent,

A compound in which R ^d4 is an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent is preferred,

R ^d1 represents a methyl group, an ethyl group, or a propyl group, and R ^d2 represents a methyl group, an ethyl group, or a propyl group,

R ^d3 represents a phenyl group substituted with a methyl group,

Compounds in which R ^d4 is a methyl group, an ethyl group, or a propyl group are more preferable,

More 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.

As compound (d3),

R ^d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent,

A compound in which R ^d2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms is preferred,

A compound in which R ^d1 is a hexyl group and R ^d2 is a phenyl group is more preferable.

[0137] Such O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) ) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3 ,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl｝-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-3-cyclopentylpropan-1-one-2-imine, etc. are mentioned. You may use commercially available products such as Irgacure OXE01, OXE02, OXE03 (manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA CORPORATION). With these O-acyloxime compounds, a blue color filter with excellent photolithographic performance tends to be obtained.

[0138] An alkylphenone compound is a compound having a structure represented by formula (d4) or a structure represented by formula (d5). * indicates a binding hand. Among these structures, the benzene ring may have a substituent.

[0139]

[0140] Compounds having a structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-( 4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane -1-one, etc. can be mentioned. You may use commercially available products such as Irgacure 369, 907, and 379 (manufactured by BASF Co., Ltd.).

Compounds having a structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxy ethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α -diethoxyacetophenone, benzyldimethylketal, etc. can be mentioned.

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

[0141] As biimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro) Phenyl)-4,4',5,5'-tetraphenylbiimidazole (see, e.g., Japanese Patent Laid-Open No. H06-75372, Japanese Patent Laid-Open No. H06-75373, etc.), 2,2'-bis ( 2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)- 4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, e.g., Japanese Patent Application Publication No. S48-38403, Japanese Patent Application Publication S62-174204, etc.), 4,4',5 , imidazole compounds in which the phenyl group at the 5'-position is substituted by a carboalkoxy group (for example, see Japanese Patent Application Laid-Open No. H07-10913, etc.). Among them, compounds represented by the following formulas or mixtures thereof are preferable.

[0142]

[0143] As triazine compounds, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- 1) ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc.

[0144] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

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, o-benzoylmethyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; Examples include 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiation aid (D1) (especially amine) described later.

[0145] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, 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). , and more preferably 5 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the blue color filter tends to improve.

[0146] [5] Polymerization initiation aid (D1)

The polymerization initiation aid (D1) is a compound or sensitizer used to promote polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When it contains a polymerization initiation aid (D1), it is used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Among them, thioxanthone compounds are preferable. You may use two or more types of polymerization initiation aids (D1) in combination.

[0147] As amine compounds, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -Dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, Examples include 4,4'-bis(ethylmethylamino)benzophenone, and among these, 4,4'-bis(diethylamino)benzophenone is preferable. You may use a commercial product such as EAB-F (manufactured by HODOGAYA CHEMICAL CO., LTD.).

[0148] As alkoxyanthracene compounds, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9, 10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

[0149] As thioxanthone compounds, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- Propoxy oxanthone, etc. can be mentioned.

[0150] As carboxylic acid compounds, phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, and dimethoxyphenylsulfanyl. Acetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

[0151] The content of the polymerization initiation aid (D1) is preferably 0.1 to 30 parts by mass, 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). am. If the content of the polymerization initiation aid (D1) is within the above range, a blue pattern can be formed with higher sensitivity, and the productivity of the blue color filter tends to improve.

[0152] [6] Thiol compound (T)

The blue curable resin composition of the present invention may contain one or two or more types 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-acyloxime compound, and/or a biimidazole compound. A thiol compound (T) is a compound that has at least one sulfanyl group (-SH) in the molecule. The thiol compound (T) is preferably a compound having one sulfanyl group in the molecule.

[0153] Compounds having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, and 2-sulfanylbenzoxa. Sol, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-Amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6- Hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanyl Pyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2- Sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2- Thiol, 2-sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5 -Sulfanyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol , 3-sulfanyl1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4-thia Diazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-sulfanyl-5-thiazolidone, 2-sulfanyl Thiazoline, 2-sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfa Nyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro- 2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthooxazole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo [ Examples include 2,4-d] pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, and 4-sulfanyl-1H-pyrazolo[2,4-d] pyrimidine.

[0154] Compounds having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediolbis(3-sulfanylpropionate), butanediolbis( 3-sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl acetate) Nylpropionate), trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris hydroxyethyl Tris(3-sulfanylpropionate), pentaerythritoltetrakis(3-sulfanylbutyrate), and 1,4-bis(3-sulfanylbutyloxy)butane.

[0155] 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 still more preferably 10 to 40 parts by mass, based on 100 parts by mass of the polymerization initiator (D). It is wealth. When the content of the thiol compound (T) is within the above range, sensitivity tends to increase and developability tends to improve.

[0156] [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-), and ether ester solvents (solvents containing -COO- and -O-). , ketone solvents (solvents containing -CO-) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0157] As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, Examples include ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

As an ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene. Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methyl anisole. etc. can be mentioned.

[0158] As ether ester solvents, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethyl Methyl methyl propionate, 3-ethoxy ethyl propionate, 2-methoxy methyl propionate, ethyl 2-methoxy propionate, 2-methoxy propyl propionate, methyl 2-ethoxy propionate, 2-ethoxy ethyl propionate, 2-methoxy -2-Methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

[0159] As ketone solvents, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentane cyclopentanone, cyclohexanone, and isophorone.

[0160] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0161] The solvent (E) preferably contains an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm in terms of coating properties and drying properties. Among them, the solvent (E) is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl. Contains at least one member selected from the group consisting of ether, 3-methoxybutylacetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide. It is preferable to use propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, and 3-ethoxyethyl propionate. It is more preferable to include at least one type selected from the group consisting of.

[0162] The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, in the blue curable resin composition. In other words, the solid content of the blue curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness during application becomes good and the color density is not insufficient when a blue color filter is formed, so the display characteristics tend to be good.

[0163] [8] Leveling agent (F)

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

[0164] Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicon DC3PA, Toray Silicon SH7PA, Toray Silicon DC11PA, Toray Silicon SH21PA, Toray Silicon SH28PA, Toray Silicon SH29PA, Toray Silicon SH30PA, Toray Silicon SH8400 (product name: manufactured by Dow Corning Toray Co., Ltd.), KP321. , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan LLC) manufacturing), etc.

[0165] Examples of fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Limited), Megapak (registered trademark) F142D, Megapak F171, Megapak F172, Megapak F173, Megapak F177, Megapak F183, Mega Park F554, Mega Park R30, Mega Park RS-718-K (manufactured by DIC CORPORATION), F-Top (registered trademark) EF301, F-Top EF303, F-Top EF351, F-Top EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd.) manufactured by Suplon (registered trademark), Suplon (registered trademark) S381, Suplon S382, Suplon SC101, Suplon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Genkyusho).

[0166] Examples of silicone-based surfactants having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megapac (registered trademark) R08, Megapac BL20, Megapac F475, Megapac F477, and Megapac F443 (manufactured by DIC CORPORATION) can be mentioned.

[0167] The content of the leveling agent (F) in the blue curable resin composition is usually 0.001 mass% or more and 0.6 mass% or less, preferably 0.002 mass% or more and 0.4 mass% or less, more preferably 0.005 mass% or more and 0.2 mass% or less. It is less than mass%. In addition, the content of the pigment dispersant is not included in the content.

[0168] [9] Antioxidant (G)

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

[0169] As phenol-based antioxidants, Irganox 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], BASF Co., Ltd. ), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Co., Ltd.), Irganox 1330 ( Irganox 1330: 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p- Cresol, manufactured by BASF Co., Ltd., Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-Trione, manufactured by BASF Co., Ltd.), Irganox 3790 (Irganox 3790: 1,3,5-tris ((4-tert-butyl-3-hydride) Roxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF Co., Ltd., Irganox 1035 (Irganox) 1035: thiodiethylenebis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Co., Ltd., Irganox 1135 (Irganox 1135: benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF Co., Ltd., Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl) )-o-cresol, manufactured by BASF Corporation), Irganox 3125 (Irganox 3125, manufactured by BASF Corporation), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6- (4-hydroxy3',5'-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF Co., Ltd., Adekastab AO-80 (Adekastab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxa Spiro(5,5)undecane, manufactured by ADEKA CORPORATION), Sumilizer BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Company, Limited), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Company, Limited), Sumilizer GS (Sumilizer GS, manufactured by Sumitomo Chemical Company, Limited), Cyanox 1790 (Cyanox 1790, manufactured by CITEC Corporation), and Vitamin E (Eisai Co., Ltd.) manufacturing), etc.

[0170] As phosphorus-based antioxidants, Irgafos 168 (Irgafos168: Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: Tris [2- [[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, manufactured by BASF Co., Ltd.) , Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Corporation, Adekastab 329K (manufactured by ADEKA CORPORATION), Adekastab PEP36 (manufactured by ADEKA CORPORATION), Adekastab PEP-8 (manufactured by ADEKA CORPORATION), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (manufactured by GENERAL ELECTRIC COMPANY), Weston 619G (manufactured by ADEKA CORPORATION) Weston 619G, manufactured by GENERAL ELECTRIC COMPANY), Ultranox 626 (Ultranox 626, manufactured by GENERAL ELECTRIC COMPANY) and Sumilizer GP: 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1.3.2]dioxaphosphepine) (manufactured by Sumitomo Chemical Company, Limited), etc.

[0171] Sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, or distearyl, and tetrakis[methylene(3-dodecylthio)propionate]methane, etc. β-alkyl mercaptopropionic acid ester compounds of polyols, etc.

[0172] The content of antioxidant (G) in the blue curable resin composition is usually 0.01% by mass or more and 5% by mass or less, preferably 0.04% by mass or more and 3% by mass or less, more preferably 0.07% by mass or more. It is less than mass%.

[0173] [10] Other ingredients

The blue curable resin composition of the present invention may optionally contain one or two or more additives such as fillers, polymer compounds other than resin (B), adhesion promoters, ultraviolet absorbers, anti-aggregation agents, organic acids, organic amine compounds, and curing agents. It may contain.

[0174] Examples of fillers include glass, silica, alumina, and the like. Examples of polymer compounds other than resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

[0175] As adhesion promoters, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N -(2-Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane and 3-mercapto Propyltrimethoxysilane, etc. can be mentioned.

[0176] As ultraviolet absorbers, benzotriazole-based compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; Benzophenone-based compounds such as 2-hydroxy-4-octyloxybenzophenone; Benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; Triazine-based compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol; etc. can be mentioned. Examples of anti-agglomeration agents include sodium polyacrylate.

[0177] Organic acids are used to adjust developability, specifically,

Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid;

Oxalic 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, Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, and mesaconic acid;

Aliphatic tricarboxylic acids such as tricarbalylic acid, aconitic acid, and camphoronic acid;

aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemellitic acid, and mesitylenic acid;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid;

Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, mellophanic acid, and pyromellitic acid; etc. can be mentioned.

[0178] As organic amine compounds,

n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n- monoalkylamines such as nonylamine, n-decylamine, n-undecylamine, and n-dodecylamine;

monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, and 4-methylcyclohexylamine;

Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine , dialkylamines such as di-tert-butylamine, di-n-pentylamine, and di-n-hexylamine;

Monoalkyl monocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;

Dicycloalkylamine such as dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine , trialkylamines such as triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, and tri-n-hexylamine. ;

dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;

monoalkyldicycloalkylamine such as methyldicyclohexylamine, ethyldicyclohexylamine, and tricyclohexylamine;

Monoalkanes such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol Allamine;

monocycloalkanolamines such as 4-amino-1-cyclohexanol;

dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, and di-n-hexanolamine;

Dicycloalkanolamines such as di(4-cyclohexanol)amine;

trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, and tri-n-hexanolamine;

Tricycloalkanolamines such as tri(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 -Aminoalkanediols such as propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, and 2-diethylamino-1,3-propanediol;

Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;

Cycloalkanone methanol containing an amino group such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;

1-Aminocyclohexanonemethanol, 4-aminocyclohexanonemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol, etc. Amino group-containing cycloalkane methanol;

β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1 -Aminocarboxylic acids such as aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid;

Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, p-n-propylaniline, p-isopropylaniline, p-n-butylaniline, p-tert-butylaniline, 1-naphthylamine , aromatic amines such as 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, and p-methyl-N,N-dimethylaniline;

Aminobenzyl alcohol such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, and p-diethylaminobenzyl alcohol;

Aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, and p-diethylaminophenol;

Aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid; etc. can be mentioned.

[0179] Examples of the curing agent include compounds that can crosslink the resin (B) by reacting with carboxyl groups in the resin (B) when heated, and compounds that can cure the blue color filter by polymerization alone. , epoxy compounds, oxetane compounds, etc. As for the hardening agent, only one type may be used, or two or more types may be used together.

[0180] As epoxy compounds, bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolak-type epoxy resins, other aromatic epoxy resins, alicyclic-based epoxy resins, Epoxy resins such as heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, and epoxidized oils, brominated derivatives of these epoxy resins, and aliphatic and cycloaliphatic resins other than epoxy resins and brominated derivatives thereof. or aromatic epoxy compounds, epoxidized products of butadiene (co)polymers, epoxidized products of isoprene (co)polymers, glycidyl (meth)acrylate (co)polymers, triglycidyl isocyanurate, etc. You can. Commercially available epoxy resins include orthocresol novolak-type epoxy resin and “Sumitoxy (registered trademark) ESCN-195XL-80” (manufactured by Sumitomo Chemical Company, Limited).

[0181] Examples of oxetane compounds include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

[0182] When the blue curable resin composition of the present invention contains an epoxy compound, an oxetane compound, etc. as a curing agent, a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. It may include . Examples of the compound include polyhydric carboxylic acid, polyhydric carboxylic acid anhydride, and acid generator.

[0183] As polyvalent carboxylic acids,

Aromatic polyvalent carboxylic acids such as 3,4-dimethylphthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and 3,3',4,4'-benzophenonetetracarboxylic acid boxylic acid;

Aliphatic polyhydric carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid;

Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentane Alicyclic polyhydric carboxylic acids such as tetracarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid; etc. can be mentioned.

[0184] As polyhydric carboxylic acid anhydride,

aromatic polyvalent carboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3',4,4'-benzophenone tetracarboxylic dianhydride;

Aliphatic polyvalent carboxylic acid anhydrides such as itaconic acid anhydride, succinic anhydride, citraconic acid anhydride, dodecenylsuccinic anhydride, tricarbalylic anhydride, maleic anhydride, and 1,2,3,4-butanetetracarboxylic dianhydride. ;

Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride alicyclic polyhydric carboxylic acid anhydrides such as water, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, and nadic anhydride;

Carboxylic acid anhydrides containing ester groups, such as ethylene glycol bistrimellitate acid and glyceroltristrimellitate anhydride; etc. can be mentioned.

[0185] As the carboxylic acid anhydride, one commercially available as an epoxy resin curing agent may be used. As an epoxy resin hardener, brand name "Adeka Hardner (registered trademark) EH-700" (manufactured by ADEKA CORPORATION), brand name "Ricacid (registered trademark) HH" (manufactured by New Japan Chemical co., ltd.), brand name "MH-" 700” (manufactured by New Japan Chemical co., ltd.).

[0186] As acid generators, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenyl·methyl·benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate , onium salts such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate.

[0187] <Method for producing blue curable resin composition>

The blue curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and, if necessary, a solvent (E), a thiol compound (T), and a leveling agent. It can be prepared by mixing (F), polymerization initiation aid (D1), antioxidant (G), and other components.

[0188] ＜Blue color filter and manufacturing method thereof, blue color filter and display device＞

The blue curable resin composition of the present invention is useful as a material for a blue color filter. A blue color filter formed from the blue curable resin composition of the present invention also falls within the scope of the present invention. The blue color filter may form a blue pattern.

Methods 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 the photolithography method is preferred. The photolithographic method is a method of applying a blue curable resin composition to a substrate, drying it to form a blue composition layer, exposing the blue composition layer through a photomask, and developing it. In the photolithographic method, a blue coating film, which is a cured product of the blue composition layer, can be formed by not using a photomask during exposure and/or not developing. A blue pattern or a 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 according to the present invention is typically used as a blue pixel.

[0189] As a substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass with a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or the above substrate. A thin film of aluminum, silver, silver/copper/palladium alloy, etc. formed on it is used. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

[0190] The formation of each color pixel by the photolithographic method can be performed using known or customary equipment and conditions, and can be produced, for example, as follows. First, the blue curable resin composition is applied on a substrate, then heated and dried (pre-bake) and/or dried under reduced pressure to remove volatile components such as solvents and dried to obtain a smooth blue composition layer. Application methods include spin coating, slit coating, and slit and spin coating.

[0191] The temperature when performing heat drying is preferably 30 to 120°C, and more preferably 50 to 110°C. Additionally, the heating time is preferably from 10 seconds to 5 minutes, and more preferably from 30 seconds to 3 minutes. When performing reduced-pressure drying, it is preferably performed under a pressure of 50 to 150 Pa and a temperature range of 20 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.

[0192] Next, the blue composition layer is exposed through a photomask to form the desired blue pattern. The pattern on the photomask is not particularly limited, and a pattern depending on the intended use is used. As a light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferable. For example, light below 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm may be selectively extracted using a band-pass filter that extracts these wavelength ranges. do.

Specifically, light sources include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

[0193] In exposure, parallel light is irradiated uniformly over the entire exposure surface, and since it is possible to perform accurate alignment between the photomask and the substrate on which the blue composition layer is formed, exposure using a mask aligner, stepper, etc. It is desirable to use the device.

[0194] A blue pattern is formed on the substrate by developing the blue composition layer after exposure by contacting it with a developer. Through development, the unexposed portion of the blue composition layer is dissolved in the developing solution and removed.

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

[0195] The development method may be any of the puddle method, dipping method, and spray method. Additionally, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

Additionally, it is preferable to post bake the obtained blue pattern. As a post-bake temperature, 150 to 250°C is preferable and 160 to 235°C is more preferable. As a post-bake time, 1 to 120 minutes is preferable, and 10 to 60 minutes is more preferable.

[0196] Since the film thickness of the obtained blue coating film affects adjacent pixels, it is desirable to be as thin as possible. When manufacturing a liquid crystal panel, especially when it is made of a thick film, light from the light source may leak through pixels of two or more colors, and there is a risk that the vividness of the colors will be lost when the panel is viewed at an angle. . Generally, the film thickness of the blue coating film after post-baking is 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 is usually 1 μm or more, and may be 1.5 μm or more. Since the blue coating film can exhibit excellent developability, it is excellent as a material for a blue color filter.

[0197] The higher the brightness of the blue coating film, the more preferable it is, preferably 8 or more, and more preferably 9 or more. The upper limit is not particularly limited, but is usually 15 or less.

[0198] The blue color filter according to the present invention is useful as a blue color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Example

[0199] Hereinafter, the present invention will be described in more detail by showing examples and comparative examples, but the present invention is not limited to these examples. In examples, % and parts indicating content or usage are based on mass, unless otherwise specified.

[0200] <Synthesis Example 1: Pigment dispersion (A1)>

C.I. Pigment Blue 15 12.1 parts

Acrylic pigment dispersant 4.2 parts

Propylene glycol monomethyl ether acetate 83.7 parts

By mixing and sufficiently dispersing the pigment using a bead mill, C.I. A pigment dispersion (A1) containing Pigment Blue 15 was obtained.

[0201] <Synthesis Example 2: Pigment dispersion (A2)>

C.I. Pigment Blue 15:6 12.0 parts

Acrylic pigment dispersant 2.0 parts

Propylene glycol monomethyl ether acetate 86.0 parts

By mixing and sufficiently dispersing the pigment using a bead mill, C.I. A pigment dispersion (A2) containing pigment blue 15:6 was obtained.

[0202] <Synthesis Example 3: Pigment dispersion (A3)>

C.I. Pigment Blue 15:3 12.1 parts

Acrylic pigment dispersant 3.6 parts

Propylene glycol monomethyl ether acetate 84.3 parts

By mixing and sufficiently dispersing the pigment using a bead mill, C.I. A pigment dispersion (A3) containing pigment blue 15:3 was obtained.

[0203] <Synthesis Example 4: Pigment dispersion (A4)>

C.I. Pigment Blue 15:4 12.1 parts

Acrylic pigment dispersant 3.6 parts

Propylene glycol monomethyl ether acetate 84.3 parts

By mixing and sufficiently dispersing the pigment using a bead mill, C.I. A pigment dispersion (A4) containing pigment blue 15:4 was obtained.

[0204] <Synthesis Example 5: Pigment dispersion (A5)>

C.I. Pigment Blue 16 12.1 parts

Acrylic pigment dispersant 5.4 parts

Propylene glycol monomethyl ether acetate 82.5 parts

By mixing and sufficiently dispersing the pigment using a bead mill, C.I. A pigment dispersion (A5) containing Pigment Blue 16 was obtained.

[0205] <Synthesis Example 6: Pigment dispersion (A6)>

C.I. Pigment Violet 23 12.0 parts

Acrylic pigment dispersant 2.0 parts

Propylene glycol monomethyl ether acetate 86.0 parts

By mixing and sufficiently dispersing the pigment using a bead mill, C.I. A pigment dispersion (A6) containing Pigment Violet 23 was obtained.

[0206] <Synthesis Example 7: Preparation of xanthene dye (A7)>

20 parts of the compound represented by the above 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 resulting solution was incubated at 110°C for 6 hours. It was stirred for a while.

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

[0207] <Synthesis Example 8: Preparation of resin (B)>

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, sufficiently flow nitrogen to create a nitrogen atmosphere, add 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate, and stir to 70°C. Heated. Next, 60 parts of methacrylic acid, 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, and the solution was added dropwise. Using a lot, it was added dropwise into a flask kept at 70°C over 4 hours.

Meanwhile, a mixed solution of 30 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 225 parts of 3-methoxybutylacetate was added dropwise into the flask over 4 hours using another dropping funnel. After completion of dropwise addition, the same temperature was maintained for 4 hours, and then cooled to room temperature to obtain a resin solution with a solid content of 32.6% by weight and an acid value of 110 mg-KOH/g (solid content conversion). The weight average molecular weight (Mw) of the resin (B) contained in the obtained resin solution was 13,400, and the molecular weight distribution was 2.50.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin (B) were measured using the GPC method under the following conditions. The ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene obtained under the following conditions was used as the molecular weight distribution.

[0208] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin (B) were measured using the GPC method under the following conditions. The ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene obtained under the following conditions was used as the molecular weight distribution.

[0209] Device: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: THF

Flow rate: 1.0mL/min

Test liquid solid concentration: 0.001 to 0.01 mass%

Injection volume: 50μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH CORPORATION)

[0210] <Examples 1 to 5 and Comparative Examples 1 to 5>

(1) Preparation of blue curable resin composition

Each pigment dispersion (A1) to (A6), xanthene dye (A7), and C.I. obtained in Synthesis Examples 1 to 6 above were used. Acid Red 52 (manufactured by Wako Pure Chemical Industries, Ltd.) (A8), C.I. expressed by the formula below: Basic Violet 10 (manufactured by Wako Pure Chemical Industries, Ltd., Rhodamine B) (A9), a resin solution containing the resin (B) obtained in Synthesis Example 8, polymerizable compound (C), polymerization initiator (Da), polymerization The initiator (Db), thiol compound (T), and leveling agent (F) were mixed in the mixing amounts shown in Table 8 to obtain a blue curable resin composition.

[0211]

[0212] In addition, when preparing the blue curable resin composition, it was mixed with propylene glycol monomethyl ether acetate so that the colorant concentration in the solid content of the blue curable resin composition was 30% by mass. The unit of the mixing amount of each component in Table 8 is “part by mass,” and the mixing amount is converted to solid content. The details of each ingredient are as follows.

[0213] [Polymerizable compounds and polymerization initiators used]

Polymerizable compound (C): Pentaerythritol triacrylate (trade name “A-TMM-3LM-N” manufactured by Shin-Nakamura Chemical Co., Ltd.),

Polymerization initiator (Da): A compound represented by the formula below.

[0214]

[0215] Polymerization initiator (Db): 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimi Dazole (brand name “TCDM” manufactured by CHEMBRIDGE INTERNATIONAL CORPORATION),

Thiol compound (T): 2-mercaptobenzothiazole (trade name “Sanshina M” manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.),

Leveling agent (F): Polyether modified silicone oil (trade name “Toray Silicone SH8400” manufactured by Dow Corning Toray Co., Ltd.).

[0216] [Table 8]

[0217] (2) Production of blue film

The blue curable resin composition was applied by spin coating on a 2 inch square glass substrate (“Eagle XG” manufactured by Corning Incorporated) and then prebaked at 100°C for 3 minutes. After cooling, the substrate onto which the blue curable resin composition was applied was irradiated with light at an exposure dose of 80 mJ/cm ² (based on 365 nm) in an air atmosphere using an exposure machine (“TME-150RSK” manufactured by TOPCON CORPORATION). did. Afterwards, post-baking was performed in an oven at 230°C for 30 minutes to obtain a blue coating film.

[0218] (3) Chromaticity evaluation

For the obtained blue coating film, spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates ( x, y) and tristimulus values (Y) were measured. The results are shown in Table 9.

[0219] [Table 9]

[0220] In Examples 1 to 5 and Comparative Examples 1 to 5, y was standardized to 0.095.

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

Claims (5)

Contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D),
The colorant (A) is a blue curable resin composition containing CI Pigment Blue 15 and a red dye or purple dye,
The red dye or purple dye contained in the colorant (A) is a compound having a xanthene skeleton,
The compound having the xanthene skeleton is a compound represented by formula (2),

[In formula (2), R ²¹ to R ²⁴ independently represent -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group are -SO ₃ ^- , - It may be substituted with 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 represents 0 or 1.
m1 represents an integer from 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.
The four R ²⁷ independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.]
A blue curable resin composition in which the content of the compound having the xanthene skeleton is 0.1 to 25% by mass based on 100% by mass of the colorant (A). A blue color filter formed from the blue curable resin composition according to claim 1. A display device comprising the blue color filter according to claim 2.

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