KR102124467B1 - Colored curable resin composition - Google Patents

Abstract

[PROBLEMS] To provide a colored curable resin composition capable of forming a color filter having good chemical resistance.
[Solutions] Colored curable resin composition containing a blue dye, resin, polymerizable compound, polymerization initiator, and silsesquioxane compound. It is preferable that the content of a silsesquioxane compound is the coloring curable resin composition of 25-3000 mass parts with respect to 100 mass parts of blue dyes of the said coloring curable resin composition.

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

Japanese Unexamined Patent Publication No. 2012-83652 discloses a colored curable resin composition comprising a blue dye, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

It has been desired to further improve the chemical resistance of the color filter formed from the colored curable resin composition.

The present invention includes the following inventions.

[1] A colored curable resin composition containing a blue dye, a resin, a polymerizable compound, a polymerization initiator, and a silsesquioxane compound.

[2] The colored curable resin composition according to [1], wherein the content of the silsesquioxane compound is 25 to 3000 parts by mass relative to 100 parts by mass of the blue dye.

[3] The blue dye according to [1] or [2], wherein the blue dye comprises at least one dye selected from the group consisting of phthalocyanine dyes, triarylmethane dyes, anthraquinone dyes, cyanine dyes, porphyrin dyes, and thiazole dyes. Colored curable resin composition.

[4] The colored curable resin composition according to [1] or [2], wherein the blue dye is a compound having an anion having at least one element and an oxygen atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus.

[5] The colored curable resin composition according to [1] or [2], wherein the blue dye contains a compound represented by formula (A-I).

In the formula (A-I), [Y ² ] ^m- represents an arbitrary m-valent anion.

R ⁴¹ to R ⁴⁴ are each independently a hydrogen atom, a C 1 to C 20 saturated hydrocarbon group which may be substituted, or a group in which an oxygen atom is inserted between carbon atoms constituting the C 2 to C 20 alkyl group, which may be substituted. It represents an aryl group or an aralkyl group which may be substituted. R ⁴¹ and R ⁴² may combine to form a ring together with the nitrogen atom to which they are attached, or R ⁴³ and R ⁴⁴ may combine to form a ring together with the nitrogen atom to which they are attached.

In each of R ⁴⁵ to R ⁵² , an oxygen atom is inserted between carbon atoms constituting a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms, respectively. The groups may be present, or R ⁴⁶ and R ⁵⁰ may combine with each other to form -O-, -NH-, -S- or -SO ₂ -.

Y ¹ represents an aryl group which may be substituted or a heteroaryl group which may be substituted.

When the compound represented by Formula (A-I) contains a plurality of cations, the plurality of cations may have the same structure or different structures.

m represents an arbitrary natural number.]

[6] A color filter formed from the colored curable resin composition according to [1] or [2].

[7] A display device comprising the color filter according to [6].

Provided is a colored curable resin composition capable of forming a color filter having good chemical resistance.

The colored curable resin composition of the present invention contains a blue dye, resin (B), polymerizable compound (C), polymerization initiator (D) and silsesquioxane compound (H).

The colored curable resin composition of the present invention may further contain a solvent (E), a thiol compound (T), an antioxidant (G), a polymerization initiator (D1), and/or a leveling agent (F), among others It is preferable to contain a solvent (E), a thiol compound (T), an antioxidant (G) and/or a leveling agent (F).

<Blue dye (A)>

In the present invention, the blue dye means a dye having a maximum absorption wavelength in a range of 580 nm or more and 650 nm or less in a chloroform solution. The blue dye is preferably a dye having a maximum absorption wavelength in a range of 590 nm or more and 645 nm or less, and more preferably a dye having a maximum absorption wavelength in a range of 600 nm or more and 645 nm or less.

As the blue dye in the present invention, a compound having a polyacid anion to be described later is also included as a compound converted from a dye having a maximum absorption wavelength in a range of 580 nm to 650 nm.

If the maximum absorption wavelength of the dye is in the range of 580 nm or more and 650 nm or less, the dye is not particularly limited, and a known dye can be used.

As a blue dye, for example, a compound classified as having a color other than a pigment in a color index (published by The Society of Dyers and Colourists), or a publicity described in a dyeing note (Shikisensha) And dyes. Moreover, according to the chemical structure, phthalocyanine dye, diarylmethane dye, triarylmethane dye, anthraquinone dye, polymethine dye, azomethine dye, cyanine dye, porphyrin dye, thiazole dye and the like can be mentioned, preferably Phthalocyanine dyes, triarylmethane dyes, anthraquinone dyes, cyanine dyes, porphyrin dyes and thiazole dyes.

Specifically,

CI Solvent Blue 2, 4, 5, 14, 18, 35, 36, 37, 43, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94 , 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 132, 136, 139;

CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45 , 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1 , 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147 , 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236 , 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

CI 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, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150 , 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195 , 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245 , 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C. I. disperse dyes such as C. I. disperse blue 1, 14, 56, 60, etc.,

CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66 , 67, 68, 81, 83, 88, 89;

CI Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, And 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84.

Examples of the blue dye include blue dyes described in International Publication No. 2012/128318, Korean Patent Publication No. 2014-0026284, Korean Patent Publication No. 2013-0111024, Korean Patent Publication No. 2013-0062510, etc. .

As the blue dye (A), a compound having an anion having at least one element and an oxygen atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus is also exemplified. As anions containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen, polyanion anions such as heteropolyacid anions having the elements and isopolyacid anions having the elements Can be lifted.

As anions of heteropolyacids or isopolyacids containing tungsten as an essential element, for example, Keggin-type phosphorus tungstate ion α-[PW ₁₂ O ₄₀ ] ^3- , Dawson-type phosphorus tungstate ion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , kegin-type tungsten silicate α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ-[ SiW ₁₂ O ₄₀ ] ^4- , and also other examples [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^{8 -} , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^{2 -} and mixtures thereof. As the anion of the heteropoly acid or isopoly acid containing tungsten as an essential element, an anion of phosphorus tungsten acid, silicung tungsten acid and tungsten-based isopoly acid is preferable.

Moreover, an anion temperature containing at least one element selected from the group consisting of silicon and phosphorus and oxygen is preferable, and examples of the anion include SiO ₃ ^{2 -} and PO ₄ ^{3 -} .

As a blue dye having an anion having at least one element and an oxygen atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, cationic having a phthalocyanine skeleton, cationic having a diarylmethane skeleton, and triarylmethane skeleton At least one cation selected from the group consisting of a cation having a cation, a cation having an anthraquinone skeleton, a cation having an azomethine skeleton, a cation having a cyanine skeleton, and a cation having a porphyrin skeleton and the anion And compounds having. As the cation having the triarylmethane skeleton, at least one aryl may be a heteroaryl such as thiazole.

As a blue dye, the compound represented by Formula (A-I) is more preferable.

In the formula (A-I), [Y ² ] ^m- represents an arbitrary m-valent anion.

R ⁴¹ to R ⁴⁴ are each independently a hydrogen atom, a C 1 to C 20 saturated hydrocarbon group which may be substituted, or a group in which an oxygen atom is inserted between carbon atoms constituting the C 2 to C 20 alkyl group, which may be substituted. It represents an aryl group or an aralkyl group which may be substituted. R ⁴¹ and R ⁴² may combine to form a ring together with the nitrogen atom to which they are attached, or R ⁴³ and R ⁴⁴ may combine to form a ring together with the nitrogen atom to which they are attached.

In each of R ⁴⁵ to R ⁵² , an oxygen atom is inserted between carbon atoms constituting a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms, respectively. The groups may be present, or R ⁴⁶ and R ⁵⁰ may combine with each other to form -O-, -NH-, -S- or -SO ₂ -.

Y ¹ represents an aryl group which may be substituted or a heteroaryl group which may be substituted.

When the compound represented by Formula (A-I) contains a plurality of cations, the plurality of cations may have the same structure or different structures.

m represents an arbitrary natural number.]

[Y ² ] ^m- represents an arbitrary m-valent anion. The anion represented by Y ² is not particularly limited as long as it is an anion capable of forming a counter ion with the dye cation, and is preferably boron-containing anion, aluminum-anion-containing, or fluorine-containing. It is an anion having a halogen atom such as an anion or a chlorine atom, and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom.

Examples of the boron anion and aluminum anion include anions represented by formula (4).

[In formula (4), W ¹ and W ² each independently represent a group having two monovalent proton donor substituents. M represents boron or aluminum.]

As a group which has two monovalent proton donor substituents, the group which proton is released from each from the compound which has at least two monovalent proton donor substituents (for example, a hydroxyl group, a carboxy group, etc.) is mentioned. Examples of the compound include catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, and 3-hydroxy-2 which may have a substituent. -Naphthoic acid, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, salicylic acid which may have a substituent, substituent It is preferable that it is benzyl acid which may have or mandelic acid which may have a substituent.

In each compound exemplified as a compound having at least two monovalent proton donating substituents, as the substituent, a saturated hydrocarbon group (for example, an alkyl group, a cycloalkyl group, etc.), a halogen atom, a hydroxy group, an amino group, a nitro group, an alkoxy And the like.

As salicylic acid which may have a substituent, salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butylsalicylic acid , Monoaminosalicylic acid such as 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6- Monohydroxysalicylic acid such as hydroxysalicylic acid (2,6-dihydroxybenzoic acid); Dihydroxysalicylic acid such as 4,5-dihydroxysalicylic acid and 4,6-dihydroxysalicylic acid; Monohalosalicylic acid such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid; Dihalosalicylic acid such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, and 3,5-diiodosalicylic acid; Trihalosalicylic acid such as 3,5,6-trichlorosalicylic acid; And the like.

As benzyl acid which may have a substituent,

As mandelic acid which may have a substituent,

And the like.

Preferred anions among the anions represented by the formula (4) are anions represented by the following formulas, and anions (BC-1) to anions (BC-24) having substituents shown in Table 1, respectively. And anions (BC-25) to anions (BC-28) represented by formulas (BC-25), formulas (BC-26), formulas (BC-27), and formulas (BC-28), and the like. .

(M represents boron or aluminum.)

(M represents boron or aluminum.)

(M represents boron or aluminum.)

(M represents boron or aluminum.)

(M represents boron or aluminum.)

Examples of the anion represented by the formula (4) are anion (BC-1), anion (BC-2), anion (BC-3), anion (BC-25), and anion (BC-26), Anion (BC-27) is preferred, anion (BC-1), anion (BC-2), and anion (BC-25) are more preferred, and anion (BC-1) and anion ( BC-2) is more preferred. Salts of any of these anions and the compound represented by formula (A-I) tend to have excellent solubility in organic solvents.

Examples of the fluorine-containing anion include groups represented by formulas (6), (7), (8), and (9).

[Wherein, in Formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a C 1-4 fluorinated alkyl group, or W ³ and W ⁴ become one and a C 1-4 fluorinated alkanediyl group. Indicates.]

[In the formula (7), W ^{5 to} W ⁷ each independently represent a fluorine atom or a C 1 to C 4 fluorinated alkyl group.]

[In formula (8), Y ^a represents a C1-C4 fluorinated alkanediyl group.]

[In formula (9), Y ^b represents a C1-C4 fluorinated alkyl group.]

In formulas (6), (7) and (9), a perfluoroalkyl group is preferable as the fluorinated alkyl group having 1 to 4 carbon atoms. Examples of the perfluoroalkyl group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , and the like.

In formulas (6) and (8), as the fluorinated alkanediyl group having 1 to 4 carbon atoms, a perfluoroalkanediyl group is preferable, and -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -and the like.

As anions represented by formula (6) (hereinafter, sometimes referred to as "anions (6)"), anions represented by formulas (6-1) to (6-6) (hereinafter, " And anion (6-1)” to “anion (6-6)”.

As an anion represented by Formula (7) (Hereinafter, it may be called "anion (7)"), Anion (7-1) represented by the following formula is mentioned.

As anions represented by formula (8) (hereinafter, sometimes referred to as "anions (8)"), anions represented by formulas (8-1) to (8-4), respectively (hereinafter, " And anion (8-1)” to “anion (8-4)”.

As anions represented by formula (9) (hereinafter, sometimes referred to as "anions (9)"), anions represented by formulas (9-1) to (9-4) (hereinafter, " And anion (9-1)” to “anion (9-4)”).

[Y ² ] ^m- is preferably a fluorine-containing anion or an ^anionic polyanate, more preferably an anion represented by formula (6), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [SiW ₁₂ O ₄₀ ] ^4- or [W ₁₀ O ₃₂ ] ^4- is preferred, more preferably anions represented by formulas (6-1) to (6-5), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , and particularly preferably an anion represented by formula (6-2), [PW ₁₂ O ₄₀ ] ^3- .

m represents an arbitrary natural number, and is equal to the negative charge of the anion [Y ² ] ^m- . The m on the cation side is determined so that the charges of the anion [Y ² ] ^m- and the cation are the same. m is preferably a natural number from 1 to 10.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁴ may be linear, branched or cyclic. Further, the saturated hydrocarbon group is preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

Examples of the linear or branched saturated hydrocarbon group include a linear alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group and decyl group; And branched chain alkyl groups such as isopropyl group, isobutyl group and 2-ethylhexyl group. The straight or branched chain saturated hydrocarbon has preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

Moreover, the said cyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

The hydrogen atom of the saturated hydrocarbon group of R ⁴¹ to R ⁴⁴ may be substituted with a substituent. As said substituent, a substituted or unsubstituted amino group or a halogen atom is mentioned. Examples of the substituted amino group include dialkylamino groups such as dimethylamino group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the saturated hydrocarbon group in which the hydrogen atom is substituted with a substituted or unsubstituted amino group or a halogen atom include groups represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

Among the groups represented by R ⁴¹ to R ⁴⁴ , examples of groups in which oxygen atoms are inserted between methylene groups (carbon atoms) constituting an alkyl group having 2 to 20 carbon atoms include groups represented by the following formula. In the following formula, * represents a bond with a nitrogen atom. Especially, as a group in which the oxygen atom is inserted between the methylene groups constituting the alkyl group, a group having 2 to 10 carbon atoms is preferable, and a group having 2 to 6 carbon atoms is more preferable. The alkyl group into which the oxygen atom is inserted is preferably a straight chain alkyl group. Moreover, as for carbon number between oxygen atoms, 1-4 are preferable and 2-3 are more preferable.

In R ⁴¹ to R ⁴⁴ , the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and preferably the aralkyl group has 7 to 20 carbon atoms, more preferably 7 to 7 carbon atoms. 10.

The aryl group of R ⁴¹ ~R ⁴⁴ may be a phenyl group, a naphthyl group, Tolu weather and the like.

Examples of the aryl group in the aralkyl group of R ⁴¹ to R ⁴⁴ include a phenyl group, a naphthyl group, and the like, and examples of the aralkyl group include a group in which a bonding group of these aryl groups and an alkanediyl group are bonded. The number of carbon atoms of the alkanediyl group is preferably 1 to 10, more preferably 1 to 5, and preferably a linear alkanediyl group. Specific examples of the alkanediyl group include a methylene group, an ethylene group, a propylene group, a butanediyl group, and a pentanediyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, and a naphthylethyl group. have.

Among the groups represented by R ⁴¹ to R ⁴⁴ , in the aryl group and aralkyl group, as the substituent, halogen atoms such as fluorine atom, chlorine atom, and iodine atom; Alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups; Hydroxy group; Alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl group; Alkoxycarbonyl groups having 2 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; And the like.

As a specific example of the aryl group which may be substituted, a group represented by the following formula is mentioned, for example. In the following formula, * represents a bond with a nitrogen atom.

Examples of the aralkyl group that may be substituted include a group in which an alkylene group such as a methylene group or an ethylene group is bonded to a bond of the aryl group.

As a ring formed by R ⁴¹ and R ⁴² bonding together with the nitrogen atom to which they are attached, and a ring formed by R ⁴³ and R ⁴⁴ bonding together with the nitrogen atom to which they are attached, a 5-membered ring such as a pyrrolidine ring ring; 6-membered rings such as morpholine ring, piperidine ring, and piperazine ring; And the like.

From the viewpoint of ease of synthesis, R ⁴¹ to R ⁴⁴ are preferably a C 1 to C 20 saturated hydrocarbon group which may be independently substituted, an aryl group which may be substituted, or an aralkyl group which may be substituted, and each independently. It is more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or a substituted aryl group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

The saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ⁴⁵ to R ⁵² may be linear, branched or cyclic, and is preferably chained. Examples of the saturated hydrocarbon group having 1 to 8 carbon atoms of R ⁴⁵ to R ⁵² include groups having 1 to 8 carbon atoms among the groups exemplified as saturated hydrocarbon groups of R ⁴¹ to R ⁴⁴ . As a group in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting the alkyl group, an alkyl group having 2 to 8 carbon atoms is more preferable. The alkyl group in which the oxygen atom is inserted is preferably a straight chain alkyl group, preferably 1 to 4 carbon atoms, and more preferably 2 to 3 carbon atoms between the oxygen atoms. For example, the group represented by the following formula is mentioned. In the following formula, * represents a bond with a carbon atom.

From the viewpoint of ease of synthesis, R ⁴⁵ to R ⁵² are preferably each independently a hydrogen atom, a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and each independently a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom. It is more preferable.

R ⁴⁶ and R ⁵⁰ may combine with each other to form -O-, -NH-, -S- or -SO ₂ -.

Y ¹ represents an aryl group which may be substituted or a heteroaryl group which may be substituted.

The aryl group may be either a monocyclic or condensed ring, and aromatic hydrocarbon groups having 6 to 20 carbon atoms such as a phenyl group, tolyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, and terphenyl group are mentioned. have.

The heteroaryl group is a substituent derived from an aromatic heterocycle. The aromatic heterocycle may be either a monocyclic or condensed ring, preferably a 5 to 10 membered ring, and more preferably a 5 to 9 membered ring.

Examples of the monocyclic aromatic heterocycle include a 5-membered ring having nitrogen atoms such as pyrrole ring, oxazole ring, pyrazole ring, imidazole ring and thiazole ring;

A 5-membered ring having an oxygen atom or a sulfur atom such as a furan ring or a thiophene ring;

A 6-membered ring having a nitrogen atom such as a pyridine ring, pyrimidine ring, pyridazine ring, or pyrazine ring; And the like. Examples of the aromatic heterocycle of the condensed ring include a condensed ring having a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, or a quinoline ring;

A ring having an oxygen atom or a sulfur atom such as a benzofuran ring; And the like. As a heteroaryl group which may be substituted, a group represented by formula (Ab2-x1) is more preferable.

[Ring T ² represents an aromatic heterocycle, preferably an aromatic heterocycle having 2 to 9 carbon atoms.

R ⁵³ and R ⁵⁴ are each independently an substituted or unsubstituted amino group or an oxygen atom inserted between carbon atoms constituting a saturated hydrocarbon group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom. Group, an aryl group which may be substituted, an aralkyl group which may be substituted, or a hydrogen atom.

R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may be substituted.

k1 represents 0 or 1.

* Represents a bond with carbocation.] Further, details of R ⁵³ to R ⁵⁵ will be described later.

As a blue dye, the compound represented by Formula (A-II) is more preferable.

In formula (A-II), [Y ² ] ^m- , R ⁴¹ to R ⁵² and m are the same as above.

R ⁵³ and R ⁵⁴ are each independently a hydrogen atom, a C1-C20 saturated hydrocarbon group which may be substituted, or a group in which an oxygen atom is inserted between carbon atoms constituting the C2-C20 alkyl group, which may be substituted. It represents an aryl group or an aralkyl group which may be substituted.

R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may be substituted.

X represents an oxygen atom, -NR ⁵⁷ -, or a sulfur atom.

R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

When the compound represented by Formula (A-II) contains a plurality of cations, the plurality of cations may have the same structure or different structures.]

As R ⁵³ , R ⁵⁴ and R ⁵⁷ , the same groups as those exemplified for R ⁴¹ to R ⁴⁴ can be mentioned.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁵⁵ include groups similar to those exemplified as saturated hydrocarbon groups of R ⁴¹ to R ⁴⁴ . Among them, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

As a group in which an oxygen atom is inserted between the carbon atoms constituting the alkyl group represented by R ⁵⁵ , groups similar to those exemplified in R ⁴¹ to R ⁴⁴ can be mentioned. The alkyl group into which the oxygen atom is inserted is preferably a straight chain alkyl group. Moreover, as for carbon number between oxygen atoms, 1-4 are preferable and 2-3 are more preferable.

In R ⁵⁵ , the aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms.

Moreover, as an aryl group of R ⁵⁵ , the group similar to the group exemplified by R ^41- R ⁴⁴ is mentioned, and a phenyl group is preferable.

In the aryl group of R ⁵⁵ , the substituent includes halogen atoms such as fluorine atom, chlorine atom, and iodine atom; Alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups; Hydroxy group; sulfamoyl group; Alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl group; Alkoxycarbonyl groups having 2 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; And the like.

R ⁵⁵ is, from the viewpoint of ease of synthesis, preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an aryl group which may be substituted, and more preferably an alkyl group having 1 to 8 carbon atoms, or a halogen atom or carbon atom 1 It is an aryl group which may be substituted with an alkoxy group of ∼4, a hydroxy group, or a methylsulfonyl group, and more preferably a group represented by the following formula. In the following formula, * represents a bond with a carbon atom.

X represents an oxygen atom, -NR ⁵⁷ -, or a sulfur atom. As a cyclic structure containing X, group represented by the following formula is mentioned, for example. In the formula, R ⁵³ to R ⁵⁵ are synonymous with the above, respectively, and * represents a bond with carbocation. Especially, as X, an oxygen atom or a sulfur atom is preferable, and a sulfur atom is especially preferable.

Examples of the cation moiety of the formula (A-I) include cation 1 to cation 27 represented by formula (A-I-1) shown in the following table, and among them, cation 1 to cation 6 And cation 12 are preferred.

In Table 2, Ph1-Ph12 shall mean the group represented by the following formula.

As the cation in the formula (A-I), cation 1 to cation 6, cation 11, or cation 12 is preferred, and cation 1, cation 2, or cation 12 is particularly preferred.

When the compound represented by Formula (A-II) contains a plurality of cations, the plurality of cations may have the same structure or different structures.

The colored curable resin composition of the present invention may contain only one type of blue dye or two or more types.

The blue dye is preferably a dye soluble in an organic solvent.

The colored curable resin composition of the present invention may contain dyes other than the blue dye. Examples of dyes other than blue dyes include azo dyes, cyanine dyes, xanthene dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline And dyes and nitro dyes.

The colored curable resin composition of the present invention is a blue dye, in addition to a compound having an anion having at least one element and an oxygen atom selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and other blue dyes or blue dyes. You may contain the dye of the.

Although the coloring curable resin composition of this invention may contain a pigment, it is preferable that it does not contain a pigment substantially. The fact that it does not contain a pigment means that the content of the pigment is 0.5% by mass or less with respect to the blue dye, and is preferably 0% by mass.

As the pigment, a known pigment can be used, and for example, a pigment classified as a pigment in the color index (published by The Society of Dyers and Colourists).

As a pigment, for example

Blue pigments such as C. I. Pigment Blue 15, 15:3, 15:4, 15:6, 60;

Violet pigments such as C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;

CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

C. I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

Red such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 Pigment; Green pigments such as C. I. Pigment Green 7, 36, 58; C. I. Pigment Brown 23, 25, and other brown pigments; And black pigments such as C. I. Pigment Black 1 and 7.

The pigment can be made into a pigment dispersion liquid in a state in which the pigment dispersant is uniformly dispersed in a solution by containing a pigment dispersant and subjecting to dispersion treatment. The pigments may be subjected to a dispersion treatment individually, or a mixture of a plurality of species may be dispersed.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by Geneca Corporation), EFKA (manufactured by BASF Corporation), And AJISPER (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemise), and the like.

The content of the blue dye is usually 1 to 100 mass%, preferably 10 to 100 mass%, more preferably 40 to 100 mass%, still more preferably 70 to 100 mass%, based on the total amount of the colorant. to be.

As a blue dye, when it includes a dye having an anion having at least one element and an oxygen atom selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and other dyes other than blue dyes or blue dyes, the anion The content of the dye having, is preferably 10 to 100 mass%, more preferably 40 to 100 mass%, and even more preferably 70 to 100 mass% with respect to the total amount of the blue dye.

The colored curable resin composition of the present invention may contain an extender pigment (I). Examples of the extender pigment include at least one selected from the group consisting of silicon oxide, barium sulfate, titanium oxide, zinc oxide, aluminum oxide, magnesium oxide and calcium carbonate. Moreover, from the point of transparency, it is preferable that the average particle diameter of the extender pigment is 500 nm or less. Among them, silicon oxide is preferred from the viewpoint of reliability and tack.

When the extender pigment is included, the content of the extender pigment (I) is preferably 0.1 to 80 parts by mass, more preferably 1 to 100 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 30 parts by mass. When the total amount of the extender pigment is in this range, the tackiness and solvent resistance tend to be improved.

<Resin (B)>

It is preferable that resin (B) is alkali-soluble resin. The alkali-soluble resin is a copolymer containing a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride.

Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1] At least one monomer (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a cyclic ether structure having 2 to 4 carbon atoms. And a copolymer having an ethylenically unsaturated bond (b) (hereinafter sometimes referred to as “(b)”);

Resin [K2] (a) and (b) and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, sometimes referred to as "(c)" Copolymer with );

Resin [K3] copolymers of (a) and (c);

Resin [K4] Resin (b) reacted with the copolymer of (a) and (c);

Resin [K5] Resin (a) reacted with the copolymer of (b) and (c);

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

Examples of (a) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hepto-2-ene, 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene , 5-carboxy-5-methylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing carboxyl groups such as [2.2.1]hepto-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride;

Unsaturated mono- or polyvalent carboxylic acid monovalent mono((meth)acryloyloxyalkyl) such as succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl] Esters;

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

Of these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution.

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

(b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

In addition, in this specification, "(meth)acrylic acid" represents at least 1 sort(s) selected from the group which consists of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

Examples of (b) include monomers having an oxiranyl group and an ethylenically unsaturated bond, monomers having an oxetanyl group and an ethylenically unsaturated bond, monomers having a tetrahydrofuryl group and an ethylenically unsaturated bond, and the like.

As (b), it is preferable that it is a monomer which has an oxiranyl group and an ethylenic unsaturated bond from the point which can make reliability, such as heat resistance and chemical resistance, of the obtained color filter higher.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate, 2 -Ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2 -Methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl(meth)acrylate (in the art, it is called "dicyclopentanyl (meth)acrylate" as a common name) In addition, it may be referred to as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decene-8-yl(meth)acrylate (in the art, as a common name It is called "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth) (Meth)acrylic acid esters such as acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

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

Bicyclo[2.2.1]hepto-2-ene, 5-methylbicyclo[2.2.1]hepto-2-ene, 5-ethylbicyclo[2.2.1]hepto-2-ene, 5-hydroxy ratio Cyclo[2.2.1]hepto-2-ene, 5-hydroxymethylbicyclo[2.2.1]hepto-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hepto-2 -Ene, 5-methoxybicyclo[2.2.1]hepto-2-ene, 5-ethoxybicyclo[2.2.1]hepto-2-ene, 5,6-dihydroxybicyclo[2.2.1]hepto -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hepto-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hepto- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hepto-2-ene, 5,6-diethoxybicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hepto-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hepto-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hepto-2-ene, 5,6-bis(cyclohexyloxy Bicarbonyl unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl- Dicarbonylimide derivatives such as 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, 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 and the like.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyl toluene, benzyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl(meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo[2.2.1]hepto-2-ene are preferred.

Specifically as the resin (B), 3,4-epoxycyclohexylmethyl(meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxycitricyclo[5.2.1.0 ^2.6 ]decyl(meth)acrylate/( Resins such as meta) acrylic acid copolymers [K1]; Glycidyl(meth)acrylate/benzyl(meth)acrylate/(meth)acrylic acid copolymer, glycidyl(meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2 .1.0 ^2.6 ]decyl(meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl(meth)acrylate/(meth)acrylic acid/ Resins such as vinyl toluene copolymer and 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; Resin such as benzyl(meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl(meth)acrylate/tricyclodecyl(meth)acrylate/(meth)acrylic acid copolymer, etc. [ K3]; A resin obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth) to a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer Resins such as resins to which acrylate is added, resins to which glycidyl (meth)acrylate is added to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer [K4]; Tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer of (meth) acrylic acid resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate of Resins such as resins in which (meth)acrylic acid is reacted with a copolymer [K5]; And resins [K6], such as resins obtained by reacting tetrahydrophthalic anhydride in addition to resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl(meth)acrylate/glycidyl(meth)acrylate. have.

The resin (B) is preferably one selected from the group consisting of resin [K1], resin [K2] and resin [K3], more preferably, the group consisting of resin [K2] and resin [K3] It is one kind selected from. If it is these resins, the coloring curable resin composition is excellent in developability. From the viewpoint of adhesion between the colored pattern and the substrate, resin [K2] is more preferable.

For example, the resin [K1] is, for example, the method described in the literature "Experiment of Polymer Synthesis" (Otsu Takayuki, published by Kagakudojin, First Edition, First Printing, published March 1, 1972) and the same It can be prepared with reference to the citations described in the literature.

The weight average molecular weight of resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film rate is also high, the solubility in the developing solution of the unexposed portion is good, and the resolution of the colored pattern tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 30 to 170 mg-KOH/g, more preferably 40 to 150 mg-KOH/g, more preferably 50 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass, based on the total amount of solids. Here, the "total amount of solid content" in the present specification means an amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid content and the content of each component thereof can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound capable of polymerizing with an active radical and/or acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and the like. Is a (meth)acrylic acid ester compound.

As a polymerizable compound having one ethylenically unsaturated bond, for example, nonylphenylcarbitolacrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitolacrylate, 2-hydroxyethyl Acrylate, N-vinylpyrrolidone, and the like (a), (b) and (c) described above.

As a polymerizable compound having two ethylenically unsaturated bonds, for example, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene Glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

Especially, it is preferable that a polymerizable compound (C) is a polymerizable compound which has three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Erythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona (meth)acrylate, tris( 2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth) Acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like, among them, di Pentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

The content of the polymerizable compound (C) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, and even more preferably 17 to 55 mass%, based on the total amount of solid content.

The content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20 on a mass basis, more preferably 35:65 to 80:20.

When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming the colored pattern and the chemical resistance of the color filter tend to improve.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. by the action of light or heat, and can initiate polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates active radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

Examples of the O-acyloxime compound 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]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3 ,3-Dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2 -Methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-3-cyclopentylpropan-1-one-2-imine. You may also use commercial items, such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA). Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) At least one member selected from the group consisting of octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred. , N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferable. If it is these O-acyloxime compounds, it tends to obtain a high brightness color filter.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl) -2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxy And oligomers of cyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethylketal. You may use commercial items, such as Irgacure 369, 907, 379 (above, BASF Corporation).

Examples of the triazine compound include 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 -Yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro Methyl)-6-[2-(3,4-dimethoxy phenyl)ethenyl]-1,3,5-triazine and the like.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use commercial items, such as Irgacure (registered trademark) 819 (manufactured by BASF).

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, 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 (for example, Japanese Patent Application Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204) Et al.), an imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted by a carboalkoxy group (for example, see JP-A No. 7-10913). Can be lifted.

Further polymerization initiators (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, o-benzoylbenzoate methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; And 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. It is preferable to use these in combination with a polymerization initiator (D1) (especially amines) described later.

As an acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenyl·methyl·benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, And onium salts such as diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylates, and benzointosylates.

As the polymerization initiator (D), a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds is preferred, and O -A polymerization initiator containing an acyloxime compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above-mentioned range, the productivity of the color filter is improved because it tends to increase the sensitivity and shorten the exposure time.

<Polymerization initiator (D1)>

The polymerization initiator (D1) is a compound or sensitizer used to accelerate polymerization of the polymerizable compound in which polymerization is initiated by the polymerization initiator. When a polymerization initiator (D1) is included, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiator (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Healer Ketone), 4,4'-bis(diethylamino)benzophenone, 4,4' -Bis(ethylmethylamino)benzophenone, etc. are mentioned, Especially, 4,4'-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

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

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxycity And oxanthone.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, and chlorophenyl And sulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

When using these polymerization initiators (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is parts by mass. When the amount of the polymerization initiator (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to improve.

<silsesquioxane compound (H)>

Silsesquioxane compound (H) means the compound represented by Formula (1) whose main chain backbone consists of Si-O bonds.

[(RSiO _{3 /2} ) _n ] (1)

(Wherein, R represents an organic group, n represents a natural number.)

R represents a monovalent organic group and examples of the monovalent organic group include monovalent hydrocarbon groups which may be substituted.

Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, and hex. And aliphatic hydrocarbon groups having 1 to 20 carbon atoms, such as a silyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group, and preferably an alkyl group having 1 to 12 carbon atoms.

Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, a benzyl group, a tolyl group, and a styryl group.

Examples of the substituent that the monovalent hydrocarbon group may have include a monovalent substituent such as a (meth)acryloyl group, a hydroxyl group, a sulfanyl group, a carboxy group, an isocyanate group, an amino group, or a ureide group. Further, -CH ₂ contained monovalent hydrocarbon groups - may be substituted with -O-, -S-, a carbonyl group or the like.

It is preferable that the monovalent organic group represented by R contains at least one reactive group. The reactive group means a group capable of reacting with other sites by a chemical reaction.

Reactive groups include vinyl groups, allyl groups, (meth)acryloyl groups, styryl groups, oxiranyl groups, oxetanyl groups, carboxy groups, hydroxy groups, thiacyclopropyl groups, sulfanyl groups, isocyanate groups, amino groups and ureido groups. It is preferable that it is a (meth)acryloyl group, a sulfanyl group, and an oxiranyl group.

The silsesquioxane compound (H) may be in the form of a basket, ladder or random, and is preferably random.

The basket-shaped silsesquioxane compound may be a complete basket shape, or an incomplete basket-shaped silsesquioxane compound such that a part of the basket is opened.

As the silsesquioxane compound (H), silsesquioxane, AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SQ described in Japanese Patent Application Laid-Open No. 2011-128239 SI-20, MAC-SQ HDM, OX-SQ TX-100, OX-SQ SI-20, OX-SQ ME-20, OX-SQ HDX (manufactured by Toa Synthetic Co., Ltd.), Conforacene (registered) Trademarks) SQ107, Conforacene (registered trademark) SQ109, Conforacene (registered trademark) SQ506, Conforacene (registered trademark) SQ502-6 (manufactured by Arakawa Chemical Industries, Ltd.) and the like.

The colored curable resin composition of this invention may contain the silsesquioxane compound (H) 2 or more types.

It is preferable that silsesquioxane compound (H) is insoluble in aqueous alkali solution.

The content of the silsesquioxane compound (H) is usually 5 to 3000 parts by mass, preferably 15 to 3000 parts by mass, more preferably 25 to 3000 parts by mass, more preferably 100 parts by mass of the blue dye It is preferably 35 to 2500 parts by mass, particularly preferably 60 to 2000 parts by mass. The higher the content of silsesquioxane with respect to the blue dye, the more significant the effect of improving chemical resistance.

<Thiol compound (T)>

Thiol compound (T) is a compound having a sulfanyl group in the molecule.

Specific examples of the thiol compound (T) include, for example, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and trimethyl Allpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydride Hydroxyethyl tristhiopropionate, pentaerythritol tetrakis(3-mercaptobutylate), 1,4-bis(3-mercaptobutyryloxy)butane, dipentaerythritol hexakisthiopropionate, dipentaerythritol Hexakis (3-mercaptobutylate), 1,3,5-trismercaptopropionate-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1 And 3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

The content of the thiol compound (T) in the colored curable resin composition of the present invention is a mass fraction relative to the total amount of the polymerization initiator (D), preferably 2 to 70 mass%, more preferably 5 to 50 mass%. . When the content of the thiol compound (T) is in the above range, the sensitivity is increased, and the developability tends to be good, which is preferable.

<Solvent (E)>

The solvent (E) is an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule, not containing -COO-), alcohol solvent (containing OH in the molecule) , Solvents not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Examples of the ester solvent are methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid And butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, propylene glycol diacetate, ethylene glycol diacetate, γ-butyrolactone, and the like. .

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and 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, phenitol, methyl anisole, etc. Can be heard.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, 3-ethoxypropionic acid ethyl, 2-methoxypropionic acid methyl, 2-methoxypropionic acid ethyl, 2-methoxypropionic acid propyl, 2-ethoxypropionic acid methyl, 2-ethoxypropionic acid ethyl, 2-methoxy-2-methyl 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 And 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.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentane And cyclohexanone, isophorone, and the like.

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

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

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

The solvent (E) is preferably an ester solvent, ether solvent, ether ester solvent or ketone solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionic acid ethyl, ethylene glycol monomethyl ether , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol or 4-hydroxy-4-methyl-2-pentanone More preferably, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-Ethoxypropionic acid ethyl or 4-hydroxy-4-methyl-2-pentanone is more preferable.

The solvent (E) may be used alone or in combination of two or more.

When two or more types of solvents are used in combination, the colored curable resin composition of the present invention preferably contains at least one selected from the group consisting of ether ester solvents and ketone solvents, and both ether ester solvents and ketone solvents are used. It is more preferable to contain 方).

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

<Leveling agent (F)>

Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

As a silicone type surfactant, surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name: manufactured by Toray Industries 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 (manufactured by Momentive Performance Materials Japan). .

As said fluorine type surfactant, surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapak (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554 , Copper R30, Copper RS-718-K (manufactured by DIC Corporation), Ftop (FTOP) (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (Mitsubishi Material Electronic Kasei Co., Ltd.), supron (Surflon) (registered trademark) S381, copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute).

As said silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Megapak (trademark) R08, copper BL20, copper F475, copper F477 and copper F443 (made by DIC Corporation) etc. are mentioned.

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, and more preferably 0.01% by mass with respect to the total amount of the colored curable resin composition. It is 0.05 mass% or less. In addition, the content of the pigment dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Antioxidant (G)>

Examples of the antioxidant (G) include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, and sulfur antioxidants, and phenolic antioxidants and phosphorus antioxidants are preferred.

The phenolic antioxidant is an antioxidant having a phenolic hydroxyl group in the molecule, and preferably has an alkyl group branched to the ortho position of the -OH group of the phenolic hydroxyl group. In this specification, an antioxidant having a phenolic hydroxyl group and a phosphoric acid ester structure or a phosphorous acid ester structure is classified as a phosphorus-based antioxidant.

As a phenolic antioxidant, for example, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 4,4'-butylidene-bis(3-methyl- 6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, (tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)pro Cypionate]methane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionate, 3,3',3",5,5',5"-hexa-t-butyl-a,a',a"-(mesitylene-2,4,6- Triyl)tri-p-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H ,3H,5H)-trione, 1,3,5-tris((4-t-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2, 4,6(1H,3H,5H)-trione, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], benzenepropanoic acid, 3,5 -Bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, 4,6-bis(octylthiomethyl)-o-cresol, Irganox (registered trademark) 3125 (manufactured by BASF), 2,4-bis(n-octylthio)-6-(4-hydroxy3',5'-di-t-butylanilino)-1,3,5-triazine, 3,9-bis(2 -(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5) Cannes, Sumiizer (registered trademark) BHT (Sumitomo Chemical Co., Ltd.), Sumi riser (registered trademark) GA-80 (Sumitomo Chemical Co., Ltd.), Sumi riser (registered trademark) GS (Sumitomo Chemical Co., Ltd.) ), Cyanox (registered trademark) 1790 (manufactured by Cytec Co., Ltd.) and vitamin E (manufactured by Azai Co., Ltd.).

An amine-based antioxidant is an antioxidant having an amino group in a molecule.

Examples of amine antioxidants include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, and p-dodecylphenyl Naphthylamine-based antioxidants such as -1-naphthylamine and phenyl-2-naphthylamine; N,N'-diisopropyl-p-phenylenediamine, N,N'-diisobutyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di -β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3- Phenylenediamine-based antioxidants such as dimethylbutyl-N'-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine, and phenyloctyl-p-phenylenediamine; Dipyridylamine, diphenylamine, p,p'-di-n-butyldiphenylamine, p,p'-di-t-butyldiphenylamine, p,p'-di-t-pentyldiphenylamine , p,p'-dioctyldiphenylamine, p,p'-dinonyldiphenylamine, p,p'-ddecyldiphenylamine, p,p'-didodecyldiphenylamine, p,p'-distyryldiphenyl Diphenyls such as amine, p,p'-dimethoxydiphenylamine, 4,4'-bis(4-α,α-dimethylbenzoyl)diphenylamine, p-isopropoxydiphenylamine and dipyridylamine Amine antioxidants; And phenothiazine-based antioxidants such as phenothiazine, N-methyl phenothiazine, N-ethyl phenothiazine, 3,7-dioctylphenothiazine, phenothiazine carboxylic acid ester, and phenoselenazine.

The phosphorus-based antioxidant is an antioxidant having a phosphoric acid ester structure or a phosphorous acid ester structure.

As the phosphorus antioxidant, for example, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d ,f][1,3,2]dioxaphosphine, tris(2,4-di-t-butylphenyl)phosphite, diphenylisooctylphosphite, 2,2'-methylenebis(4,6- Di-tert-butylphenyl)octylphosphite, diphenylisodecylphosphite, diphenylisodecylphosphite, triphenylphosphate, tributylphosphate, distearylpentaerythritol diphosphite, cyclic neopentanetetraylbis(2 ,6-di-t-butyl-4-methylphenyl)phosphite, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra -t-butylbenzo[d,f][1,3,2]dioxaphosphine, tris(nonylphenyl)phosphite, tris(mono-&dinonylphenyl mixed)phosphite, diphenylmono(tridecyl )Phosphite, 2,2'-ethylidenebis(4,6-di-t-butylphenol)fluorophosphite, phenyldiisodecylphosphite, tris(2-ethylhexyl)phosphite, tris(isodecyl) )Phosphite, tris(tridecyl)phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene-di-phosphonite, 4,4'-isopropyly Dendiphenyltetraalkyl(C12-C15)diphosphite, 4,4'-butylidenebis(3-methyl-6-t-butylphenyl)-ditridecylphosphite, bis(nonylphenyl)pentaerythritoldiphosphite, Bis(2,4-di-t-butylphenyl)pentaerythritol-di-phosphite, cyclic neopentanetetraylbis(2,6-di-t-butyl-4-methylphenyl-phosphite), 1,1 ,3-tris(2-methyl-4-ditridecylphosphite-5-t-butylphenyl)butane, tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'-ratio Phenylenediphosphonite, tri-2-ethylhexylphosphite, triisodecylphosphite, tristearylphosphite, phenyldiisodecylphosphite, trilauryl trithiophosphite, distearylpentaerythritol diphosphite, Tris(nonylatedphenyl)phosphite tris[2-[[2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl ]Oxy]ethyl]amine, bis(2,4-bis(1,1-dimethylethyl)-6 -Methylphenyl) ethyl ester phosphorous acid, Adekastab (registered trademark) 329K (manufactured by ADEKA Corporation), Adekastab (registered trademark) PEP36 (manufactured by ADEKA Corporation), Adekastab (registered trademark) PEP-8 ( ADEKA Corporation), Sandstab (registered trademark) P-EPQ (manufactured by Client), Weston (registered trademark) 618 (made by GE), Weston (registered trademark) 619G (made by GE), Ultranox ( Trademark) 626 (manufactured by GE), 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz and [d,f][1,3,2]dioxaphosphine.

The sulfur-based antioxidant is an antioxidant having a sulfur atom in its molecule.

Examples of sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionic acid, dimyristyl or distearyl, tetrakis[methylene(3-dodecylthio)propionate]methane, and the like. And β-alkyl mercaptopropionic acid ester compounds of polyols.

The colored curable resin composition of the present invention may contain two or more antioxidants.

The content of the antioxidant (G) in the present invention is usually 0.1 to 10% by mass, preferably 0.5 to 8% by mass, more preferably 1 to 6% by mass, based on the total amount of solids. If it is in the said range, it is preferable from the point which it disperse|distributes favorably in a coloring curable resin composition, and precipitation of unnecessary components is few and it is hard to influence the color characteristic of the color filter obtained.

<Other ingredients>

The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, light stabilizers, and chain transfer agents, if necessary.

<Production method of colored curable resin composition>

The colored curable resin composition of the present invention is used, for example, as a blue dye (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a silsesquioxane compound (H), and if necessary It can be prepared by mixing a solvent (E), a leveling agent (F), an antioxidant (G), a polymerization initiator (D1), a thiol compound (T), a pigment, and other components.

When a pigment is included, it is preferable that the pigment is mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 µm or less. At this time, part or all of the pigment dispersant and the resin (B) may be blended as necessary. A desired colored curable resin composition can be prepared by mixing the pigment dispersion obtained in this way so that the remaining components are at a predetermined concentration.

The dye may be dissolved in part or all of the solvent (E), respectively, to prepare a solution in advance, or may be dispersed in part or all of the solvent (E) to prepare a dye dispersion in advance. When preparing a dye dispersion, you may use the dispersing agent used in this field. It is preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 µm.

It is preferable to filter the colored curable resin composition after mixing with a filter having a pore diameter of about 0.01 to 10 µm.

<Manufacturing method of color filter>

As a method of manufacturing a colored pattern with the colored curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, and the like can be mentioned. Especially, the photolithography method is preferable. The photolithography method is a method of applying the colored curable resin composition to a substrate, drying it to form a colored composition layer, exposing and developing the colored composition layer via a photomask. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed by not using and/or developing a photomask during exposure. The colored pattern or colored coating formed as described above is the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted depending on the purpose or use, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass with silica coating on the surface, resin plates such as polycarbonate, methyl polymethacrylate, polyethylene terephthalate, silicon, and aluminum on the substrate, What formed silver, silver/copper/palladium alloy thin film, etc. is used. Separate color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithography method can be carried out by a known or common apparatus or condition. For example, it can be manufactured as follows.

First, a colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed and dried by heating drying (pre-baking) and/or drying under reduced pressure to obtain a smooth colored composition layer.

As a coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. are mentioned.

The temperature in the case of heating and drying is preferably 30 to 120°C, and more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferable to carry out in a temperature range of 20 to 25°C under a pressure of 50 to 150 Pa.

The thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the said photomask is not specifically limited, The pattern according to the intended use is used.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light having a wavelength of less than 350 nm is cut using a filter that cuts this wavelength region, or a bandpass filter that extracts light near 436 nm, around 408 nm, and around 365 nm using these wavelength regions You may take it out selectively. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper, because it is possible to uniformly irradiate parallel light beams over the entire exposure surface or to accurately align the photomask and the substrate on which the colored composition layer is formed.

A colored pattern is formed on the substrate by developing the colored composition layer after exposure by contacting it with a developer. By development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any of paddle method, dipping method and spray method. Further, the substrate may be tilted at an arbitrary angle during development.

After development, it is preferable to wash with water.

Moreover, it is preferable to post-bak to the obtained coloring pattern. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

According to the colored curable resin composition of the present invention, a color filter particularly excellent in brightness can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic papers, etc.) and solid-state imaging devices. Especially, it is useful as a color filter for liquid crystal display devices.

[Example]

Hereinafter, the colored curable resin composition of this invention is demonstrated in detail by an Example. "%" and "part" in the example are mass% and mass parts unless otherwise specified.

In the following synthesis examples, the compounds were identified by mass spectrometry (LC; 1200 type (Agilent type), MASS; LC/MSD type (Agilent type)) or elemental analysis (VARIO-EL manufactured by Elementar Corporation). (同定).

[Synthesis Example 1]

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 36.3 parts of potassium thiocyanate and 160 parts of acetone were added, followed by stirring at room temperature for 30 minutes. Subsequently, 50 parts of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and stirred at room temperature for 2 hours. After the obtained reaction mixture was ice-cooled, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and stirred at room temperature for 30 minutes. After ice-cooling the obtained reaction mixture, 34.2 parts of 30% sodium hydroxide aqueous solution was added dropwise, and further stirred at room temperature for 30 minutes. To the obtained reaction mixture, 35.3 parts of chloroacetic acid was added dropwise at room temperature, stirred under heated reflux for 7 hours, and allowed to cool to room temperature. The obtained reaction solution was added in 120 parts of water, and 200 parts of toluene was further added and stirred for 30 minutes. The obtained solution was separated into an organic layer and a water layer by separating operation, and the obtained organic layer was washed with 200 parts of 1 regular hydrochloric acid, followed by washing with water, and finally with saturated brine. An appropriate amount of manganese was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a solvent to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60° C. to obtain 52.0 parts of a compound represented by formula (B-I-1). Yield 50%

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 9.3 parts of the compound represented by formula (BI-1), 10 parts of 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene After 20 parts were added, 14.8 parts of phosphorus oxychloride were added, followed by stirring at 95 to 100°C for 3 hours. After the reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropanol. After the obtained diluted reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and a water layer by a separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of forget-me-not was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a solvent to obtain a blue-violet solid. The obtained blue-violet solid was dried under reduced pressure at 60° C. to obtain 19.8 parts of the compound represented by formula (A-II-1). Yield 100%

Identification of the compound represented by formula (A-II-1)

(Mass spectrometry) ionization mode = ESI +: m/z = 601.3 [M-Cl] ⁺

Exact Mass: 636.3

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10 parts of the compound represented by formula (A-II-1), bis(trifluoromethanesulfonyl)imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.5 parts, And 100 parts of N,N-dimethylformamide, and then stirred at 50-60°C for 3 hours. After the obtained reaction mixture was cooled to room temperature, 2000 parts of water was added dropwise while stirring for 1 hour to obtain a dark blue suspension. The suspension obtained was filtered to give a turquoise solid. The obtained turquoise solid was dried under reduced pressure at 60° C. to obtain 11.3 parts of the compound represented by formula (A-I-1). Yield 82%

0.35 g of the compound represented by formula (A-I-1) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with chloroform to make a volume of 100 cm 3 (concentration: 0.028 g/L), The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound exhibited an absorbance of 2.9 (arbitrary unit) at λmax = 628 nm.

[Synthesis Example 2]

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 32.2 parts of potassium thiocyanate and 160 parts of acetone were added, followed by stirring at room temperature for 30 minutes. To the obtained mixture, 50 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and stirred at room temperature for 2 hours. The obtained reaction mixture was ice-cooled. 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained reaction mixture, and stirred at room temperature for 30 minutes. The obtained reaction mixture was ice-cooled, 34.2 parts of 30% sodium hydroxide aqueous solution was added dropwise, and further stirred at room temperature for 30 minutes. To the obtained mixture, 31.3 parts of chloroacetic acid was added dropwise at room temperature and stirred under reflux for 7 hours. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120 parts of water, and then 200 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and a water layer by separating operation, and the obtained organic layer was washed with 1 regular hydrochloric acid, then washed with water, and finally washed with saturated brine. An appropriate amount of forget-me-not was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a solvent to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60° C. to obtain 49.9 parts of the compound represented by formula (B-I-2). Yield 51%

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 9.9 parts of the compound represented by formula (BI-2), 10 parts of 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene After 20 parts were added, 14.8 parts of phosphorus oxychloride were added, followed by stirring at 95 to 100°C for 3 hours. After the reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropanol. After the obtained diluted reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and a water layer by a separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of forget-me-not was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a evaporator to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60° C. to obtain 17.2 parts of the compound represented by formula (A-II-2). Yield 85%

Identification of the compound represented by formula (A-Ⅱ-2)

(Mass spectrometry) ionization mode = ESI +: m/z = 619.3 [M-Cl] ⁺

Exact Mass: 654.3

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10 parts of a compound represented by formula (A-II-2), 5.7 parts of bis(trifluoromethane sulfonyl)imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), And 30 parts of N,N-dimethylformamide, and stirred at 40°C for 3 hours. After the obtained reaction mixture was cooled to room temperature, 500 parts of water was added dropwise while stirring for 1 hour to obtain a dark blue suspension. The suspension obtained was filtered to give a turquoise solid. The obtained turquoise solid was dried under reduced pressure at 60° C. to obtain 11.9 parts of the compound represented by formula (A-I-2). Yield 86%

0.35 g of the compound represented by formula (A-I-2) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with chloroform to make a volume of 100 cm 3 (concentration: 0.028 g/L), The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound exhibited an absorbance of 3.1 (arbitrary unit) at λmax = 630 nm.

[Synthesis Example 3]

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 23.3 parts of potassium thiocyanate and 160 parts of acetone were added, followed by stirring at room temperature for 30 minutes. To the obtained mixture, 50 parts of 2-bromobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and further stirred at room temperature for 2 hours. After the obtained reaction mixture was ice-cooled, 29.3 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture, and stirred at room temperature for 30 minutes. After the obtained reaction mixture was ice-cooled, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise, and stirred at room temperature for 30 minutes. To the obtained mixture, 22.6 parts of chloroacetic acid was added dropwise at room temperature, followed by stirring under reflux for 7 hours. After the obtained reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120 parts of water, and then 200 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and a water layer by separating operation, and the obtained organic layer was washed with 1 regular hydrochloric acid, washed with water, and finally washed with saturated brine. An appropriate amount of manganese was added to the obtained organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a solvent to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60° C. to obtain 41.6 parts of a compound represented by formula (B-I-3). Yield 45%

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 12.9 parts of a compound represented by formula (BI-3), 10 parts of 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene After 20 parts were added, 14.8 parts of phosphorus oxychloride were added, followed by stirring at 95 to 100°C for 3 hours. After the reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropanol. After the obtained diluted reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and a water layer by a separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of manganese was added to the obtained organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a solvent to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60° C. to obtain 17.6 parts of the compound represented by formula (A-II-3). Yield 80%

Identification of the compound represented by formula (A-Ⅱ-3)

(Mass spectrometry) ionization mode = ESI +: m/z = 679.3 [M-Cl] ⁺

Exact Mass: 714.2

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10 parts of the compound represented by formula (A-II-3), 5.2 parts of bis(trifluoromethanesulfonyl)imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), And 30 parts of N,N-dimethylformamide, and stirred at 40°C for 3 hours. After the obtained reaction mixture was cooled to room temperature, 500 parts of water was added dropwise while stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a turquoise solid. The obtained turquoise solid was dried under reduced pressure at 60° C. to obtain 12.9 parts of the compound represented by formula (A-I-3). Yield 96%

0.35 g of the compound represented by formula (A-I-3) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with chloroform to make a volume of 100 cm 3 (concentration: 0.028 g/L), The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound exhibited an absorbance of 2.6 (arbitrary units) at λmax = 632 nm.

[Synthesis Example 4]

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 33 parts of potassium thiocyanate and 160 parts of acetone were added, followed by stirring at room temperature for 30 minutes. To the obtained mixture, 50.0 parts of 2-methylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and stirred at room temperature for 2 hours. After the obtained reaction mixture was ice-cooled, 41.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture, and stirred at room temperature for 30 minutes. After the obtained reaction mixture was ice-cooled, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise, and stirred at room temperature for 30 minutes. To the obtained mixture, 32.1 parts of chloroacetic acid was added dropwise at room temperature and stirred under reflux for 7 hours. The obtained reaction mixture was allowed to cool to room temperature, and the obtained solution was poured into 120 parts of water, and then 200 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and a water layer by separating operation, and the obtained organic layer was washed with 1 regular hydrochloric acid, washed with water, and finally washed with saturated brine. An appropriate amount of forget-me-not was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a solvent to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60° C. to obtain 40.5 parts of a compound represented by formula (B-I-4). Yield 41%

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 9.7 parts of the compound represented by formula (BI-4), 10 parts of 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), and After adding 20 parts of toluene, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100°C for 3 hours. After the reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropanol. After the obtained diluted reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and a water layer by a separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of forget-me-not was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a solvent to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60° C. to obtain 15.1 parts of the compound represented by formula (A-II-4). Yield 75%

Identification of the compound represented by formula (A-Ⅱ-4)

(Mass spectrometry) ionization mode = ESI +: m/z = 615.4 [M-Cl] ⁺

Exact Mass: 650.3

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10 parts of the compound represented by formula (A-II-4), 5.7 parts of bis(trifluoromethanesulfonyl)imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), And 30 parts of N,N-dimethylformamide, and stirred at 40°C for 3 hours. After the obtained reaction mixture was cooled to room temperature, 500 parts of water was added dropwise while stirring for 1 hour to obtain a dark blue suspension. The suspension obtained was filtered to give a turquoise solid. The obtained turquoise solid was dried under reduced pressure at 60° C. to obtain 13.2 parts of the compound represented by formula (A-I-4). Yield 96%

0.35 g of the compound represented by formula (A-I-4) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with chloroform to make a volume of 100 cm 3 (concentration: 0.028 g/L), The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound exhibited an absorbance of 2.7 (arbitrary unit) at λmax = 627 nm.

[Synthesis Example 5]

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 24.5 parts of potassium thiocyanate and 160 parts of acetone were added, followed by stirring at room temperature for 30 minutes. To the obtained mixture, 50 parts of 2-trifluoromethylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and stirred at room temperature for 2 hours. After the obtained reaction mixture was ice-cooled, 30.8 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture, and stirred at room temperature for 30 minutes. The obtained reaction mixture was ice-cooled. 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise to the obtained mixture, and stirred at room temperature for 30 minutes. To the obtained mixture, 23.8 parts of chloroacetic acid was added dropwise at room temperature, followed by stirring under reflux for 7 hours. The obtained reaction mixture was allowed to cool to room temperature, poured into 120 parts of water, and then 200 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and a water layer by separating operation, and the obtained organic layer was washed with 1 regular hydrochloric acid, washed with water, and finally washed with saturated brine. An appropriate amount of manganese was added to the obtained organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a solvent to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60° C. to obtain 31.1 parts of the compound represented by formula (B-I-5). Yield 36%

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 11.4 parts of a compound represented by formula (BI-5), 10 parts of 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), and After adding 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100°C for 3 hours. After the reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropanol. After the obtained diluted reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and a water layer by a separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of forget-me-not was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a solvent to obtain a blue-violet solid. The obtained blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60° C. to obtain 15.2 parts of the compound represented by formula (A-II-5). Yield 70%

Identification of the compound represented by formula (A-Ⅱ-5)

(Mass spectrometry) ionization mode = ESI +: m/z = 669.3 [M-Cl] ⁺

Exact Mass: 704.3

The following reaction was performed under nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10 parts of the compound represented by formula (A-II-5) and 4.1 parts of bis(trifluoromethane sulfonyl)imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) , And N,N-dimethylformamide was added 30.0 parts, followed by stirring at 40°C for 3 hours. After the obtained reaction mixture was cooled to room temperature, 500 parts of water was added dropwise while stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a turquoise solid. The resulting turquoise solid was dried under reduced pressure at 60° C. to obtain 11.4 parts of the compound represented by formula (A-I-5). Yield 85%

0.35 g of the compound represented by formula (A-I-5) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with chloroform to make a volume of 100 cm 3 (concentration: 0.028 g/L), The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound exhibited an absorbance of 1.9 (arbitrary unit) at λmax = 631 nm.

[Synthesis Example 6]

The following reaction was performed under nitrogen atmosphere. 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide were added to a flask equipped with a cooling tube and a stirring device, and the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) under ice cooling was added in small portions over 30 minutes, followed by stirring for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added to the reaction solution and stirred at room temperature for 24 hours. After adding the reaction solution little by little to 200 parts of ice water, it stood at room temperature for 15 hours, and when water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, it was stirred at room temperature for 15 hours. The precipitated solid was separated by filtration, and then purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60° C. to obtain 9.8 parts of the compound represented by formula (C-I-18).

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 8.2 parts of the compound represented by formula (B-I-2), 10 parts of compound represented by formula (C-I-18) and 20 parts of toluene were added, and then 12.2 parts of phosphorus oxychloride was added and stirred at 95 to 100°C for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, stirring was stopped, and after standing for 30 minutes, the organic layer and the water layer were separated. After the aqueous layer was discarded by separating, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of forget-me-not was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with a solvent by an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried under reduced pressure at 60° C. to obtain 18.4 parts of the compound represented by formula (A-II-18).

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 8 parts of the compound represented by formula (A-II-18) and 396 parts of methanol were added, followed by stirring at room temperature for 30 minutes to prepare a blue solution. Subsequently, 396 parts of water was added to the blue solution, followed by stirring at room temperature for 30 minutes to obtain a reaction solution.

53 parts of water was added to a beaker, and 11.8 parts of keggin-type tungsten acid (manufactured by Aldrich) and 53 parts of methanol were added into the water, and mixed under air atmosphere at room temperature to prepare a phosphorus tungsten acid solution.

The obtained phosphorus tungsten acid solution was dripped over 1 hour in the reaction solution prepared first. After stirring at room temperature for 30 minutes, it was filtered to obtain a blue solid. The obtained blue solid was poured into 200 parts of methanol, dispersed for 1 hour, and then the operation of filtering was repeated twice. The blue solid obtained by the above operation was poured into 200 parts of water, dispersed for 1 hour, and then the filtering operation was repeated twice. The blue solid obtained by the above operation was dried under reduced pressure at 60°C to obtain 17.1 parts of the compound represented by formula (A-I-18).

0.35 g of the compound represented by formula (A-I-18) was dissolved in chloroform to make a volume of 250 cm 3, of which 2 cm 3 was diluted with chloroform to make a volume of 100 cm 3 (concentration: 0.028 g/L), The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). This compound exhibited an absorbance of 1.1 (arbitrary units) at λmax = 626 nm.

[Synthesis Example 7]

In a flask equipped with a stirrer, a thermometer, a reflux cooler, and a dropping funnel, nitrogen was flowed at 0.02 L/min into a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added and heated to 70°C while stirring. Subsequently, 60 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate (compound represented by formula (I-1) and compound represented by formula (II-1), in molar ratio, 50 : It was mixed at 50.) 440 parts were dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution, and the solution was dropped into a flask kept at 70°C over 4 hours using a dropping funnel.

On the other hand, a solution in which 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of propylene glycol monomethyl ether acetate was dropped into the flask over 4 hours using a separate dropping funnel. . After the dropping of the polymerization initiator solution was completed, the mixture was maintained at 70°C for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1×10 ³ , molecular weight distribution was 2.16, solid content was 34.8%, and solid content was converted. To obtain a resin B1 solution having an acid value of 81 mg-KOH/g. Resin B1 has the structural unit shown below.

[Synthesis Example 8]

The flask was equipped with a reflux cooler, a dropping funnel, and a stirrer, and nitrogen was flowed in an appropriate amount to replace it with a nitrogen atmosphere, and 371 parts by weight of propylene glycol monomethyl ether acetate was added and heated to 85°C while stirring. Subsequently, 54 parts by weight of acrylic acid, 225 parts by weight of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8 or/and 9-ylacrylate, 81 parts by weight of vinyltoluene (isomer mixture), propylene A mixed solution of 80 parts by weight of glycol monomethyl ether acetate was added dropwise over 4 hours.

On the other hand, a mixed solution in which 30 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 160 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin B2) having a B-type viscosity (23°C) of 246 mPas, a solid content of 37.5% by weight, and a solution acid value of 43 mg-KOH/g. . The weight average molecular weight Mw of the resin B2 was 1.1×10 ⁴ and molecular weight distribution 2.01. Resin B2 has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resins obtained in Synthesis Examples 7 and 8 were measured under the following conditions using the GPC method.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL/min

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

The ratio (Mw/Mn) of the weight average molecular weight and number average molecular weight in terms of polystyrene obtained above was referred to as molecular weight distribution.

Preparation Example 1

<Preparation of dispersion (1)>

10 parts of the compound represented by formula (A-I-18), 2 parts of dispersant (BYK (registered trademark)-LPN6919 (manufactured by BYK) Chemie Japan), 4 parts of resin B2 (in terms of solid content) and propylene glycol mono Dispersion liquid (1) was obtained by mixing 84 parts of methyl ether acetate and sufficiently dispersing the compound represented by formula (A-I-18) using a bead mill.

Examples 1-12 and Comparative Example 1

<Preparation of colored curable resin composition>

Each component of Table 3 and Table 4 was mixed to obtain a colored curable resin composition. In Tables 3 and 4, the number of resins represents the value in terms of solid content.

In addition, in Table 3 and Table 4, each component shows the following.

Blue dye (A):

A1; Compound represented by formula (A-I-1)

A2; Compound represented by formula (A-I-2)

A3; Compound represented by formula (A-I-3)

A4; Compound represented by formula (A-I-4)

A5; Compound represented by formula (A-I-5)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)

Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

Antioxidant (G): 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f ][1,3,2]Dioxaphosphine (Sumirizu (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H1; Konposeran (registered trademark) SQ109; Arakawa Chemical Industry Co., Ltd.

Silsesquioxane compound (H): H2; AC-SQ TA-100; Doa Synthetic

Solvent (E): E1: Propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Industries Co., Ltd.)

<Production of coloring pattern>

On a 5 cm edge glass substrate (Eagle XG; manufactured by Corning), the colored curable resin composition was applied by a spin coating method, and then prebaked at 100° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the coloring composition layer was formed and the photomask made of quartz glass was set to 100 µm, and an exposure amount of 150 mJ/cm 2 in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) ( 365 nm). As a photomask, a 100 µm line and space pattern was used. The colored composition layer after light irradiation was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 80C for 80 seconds, and after washing with water, it was post-baked in an oven at 230C for 20 minutes. By doing so, a colored pattern was obtained.

<Film thickness measurement>

About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Japan Vacuum Technology Co., Ltd. product). Table 5 shows the results.

<Chemical resistance evaluation>

About the obtained coloring pattern, spectroscopy is measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y in the XYZ colorimeter of CIE using the characteristic function of the C light source) ) And the tristimulus value Y were measured.

The resulting coloring pattern was immersed in N-methylpyrrolidone at 23°C for 40 minutes. After immersion, the xy chromaticity coordinates (x, y) and Y were measured in the same manner as before immersion, and the color difference ΔEab* was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Calculation method of color difference). Based on ΔEab* of the colored curable composition obtained in Comparative Example 1, the improvement rate of chemical resistance was calculated according to the following formula. Table 5 shows the results.

Improvement rate (%) = {(△Eab* in Comparative Example 1-△Eab* in Example) / △Eab* in Comparative Example 1} × 100

Examples 13 to 16 and Comparative Example 2

<Preparation of colored curable resin composition>

Each component in Table 6 was mixed to obtain a colored curable resin composition. In Table 6, the number of resins represents the value in terms of solid content.

In addition, in Table 6, each component shows the following.

Blue dye (A); A6: C. I. Basic Blue 7 (Tokyo Kasei Co., Ltd., maximum absorption wavelength in chloroform solution; 631 nm)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)

Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

Antioxidant (G): 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f ][1,3,2] Dioxaphosphine (Sumirizu (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H1; Konposeran (registered trademark) SQ109; Arakawa Chemical Industry Co., Ltd.)

Solvent (E): E1: Propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Industries Co., Ltd.)

A coloring pattern was prepared in the same manner as in Example 1, and chemical resistance evaluation was performed. Based on ΔEab* of the colored curable composition obtained in Comparative Example 2, the improvement rate of chemical resistance was calculated according to the following formula. Table 7 shows the results.

Improvement rate (%) = {(△Eab* in Comparative Example 2-△Eab* in Example) / △Eab* in Comparative Example 2) × 100

Examples 17-20 and Comparative Example 3

<Preparation of colored curable resin composition>

Each component in Table 8 was mixed to obtain a colored curable resin composition. In Table 8, the number of resins represents the value in terms of solid content.

In addition, in Table 8, each component shows the following.

Blue dye (A);

A7: A mixture of compounds represented by formulas (3-1), (3-2), (3-3), and (3-4) (prepared by a method according to the synthetic example of Japanese Patent No. 3961078). Maximum absorption wavelength in chloroform solution; 594 nm)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)

Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

Antioxidant (G): 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f ][1,3,2] Dioxaphosphine (Sumirizu (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H1; Konposeran (registered trademark) SQ109; Arakawa Chemical Industry Co., Ltd.

Solvent (E): E1: Propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Industries Co., Ltd.)

A coloring pattern was prepared in the same manner as in Example 1, and chemical resistance evaluation was performed. Based on ΔEab* of the colored curable composition obtained in Comparative Example 3, the improvement rate of chemical resistance was calculated according to the following formula. Table 9 shows the results.

Improvement rate (%) = {(ΔEab* in Comparative Example 3-ΔEab* in Example) ／ ΔEab* in Comparative Example 3} × 100

Examples 21-24 and Comparative Example 4

<Preparation of colored curable resin composition>

Each component of Table 10 was mixed to obtain a colored curable resin composition. In Table 10, the number of resins represents the value in terms of solid content.

In addition, in Table 10, each component shows the following.

Blue dye (A): A8; CERAFIS BLUE 603 (Maximum absorption wavelength in chloroform solution manufactured by Orient Chemical Industries, Ltd.; 611 nm)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)

Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

Antioxidant (G): 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f ][1,3,2] Dioxaphosphine (Sumirizu (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H2; AC-SQ TA-100; Doa Synthetic Co., Ltd.)

Solvent (E): E1: Propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Industries Co., Ltd.)

A coloring pattern was prepared in the same manner as in Example 1, and chemical resistance evaluation was performed. Based on ΔEab* of the colored curable composition obtained in Comparative Example 4, the improvement rate of chemical resistance was calculated according to the following formula. Table 11 shows the results.

Improvement rate (%) = {(ΔEab* in Comparative Example 4-ΔEab* in Example) ／ ΔEab* in Comparative Example 4} × 100

Examples 25-28 and Comparative Example 5

<Preparation of colored curable resin composition>

Each component in Table 12 was mixed to obtain a colored curable resin composition. In Table 12, the number of resins represents the value in terms of solid content.

In addition, in Table 12, each component shows the following.

Blue dye (A): A9; C. I. Solvent Blue 45 (Savinyl Blue RS; manufactured by Clariant, maximum absorption wavelength in chloroform solution; 625 nm)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)

Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

Antioxidant (G): 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f ][1,3,2] Dioxaphosphine (Sumirizu (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H1; Konposeran (registered trademark) SQ109; Arakawa Chemical Industry Co., Ltd.

Solvent (E): E1: Propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Industries Co., Ltd.)

A coloring pattern was prepared in the same manner as in Example 1, and the obtained coloring pattern was immersed in N-methylpyrrolidone at 40°C for 30 minutes to evaluate chemical resistance. Based on ΔEab* of the colored curable composition obtained in Comparative Example 5, the improvement rate of chemical resistance was calculated according to the following formula. Table 13 shows the results.

Improvement rate (%) = {(ΔEab* in Comparative Example 5-ΔEab* in Example) ／ ΔEab* in Comparative Example 5} × 100

Examples 29-32 and Comparative Example 6

<Preparation of colored curable resin composition>

Each component in Table 14 was mixed to obtain a colored curable resin composition. In the table, the number of resins represents the value in terms of solid content.

In addition, in Table 14, each component shows the following.

Dispersion (1): Dispersion (1) prepared in Preparation Example 1

Resin (B): Resin B2

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)

Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

Silsesquioxane compound (H): H1; Konposeran (registered trademark) SQ109; Arakawa Chemical Industry Co., Ltd.

Solvent (E): E1: Propylene glycol monomethyl ether acetate

Solvent (E): E3: Propylene glycol monomethyl ether

Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Industries Co., Ltd.)

<Chemical resistance evaluation>

About the obtained coloring pattern, spectroscopy is measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y in the XYZ colorimeter of CIE using the characteristic function of the C light source) ) And the tristimulus value Y were measured.

The resulting coloring pattern was immersed in N-methylpyrrolidone at 23°C for 30 minutes. After immersion, the xy chromaticity coordinates (x, y) and Y were measured in the same manner as before immersion, and the color difference ΔEab* was calculated by the method described in JIS Z 8730:2009 (7. Calculation method of color difference). Based on ΔEab* of the colored curable composition obtained in Comparative Example 6, the improvement rate of chemical resistance was calculated according to the following formula. Table 15 shows the results.

Improvement rate (%) = {(△Eab* in Comparative Example 6-ΔEab* in Example) / △Eab* in Comparative Example 6} × 100

Examples 33-36 and Comparative Example 7

<Preparation of colored curable resin composition>

The components of Table 16 were mixed to obtain a colored curable resin composition. In the table, the number of resins represents the value in terms of solid content.

In addition, in Table 16, each component shows the following.

Dispersion (1): Dispersion (1) prepared in Preparation Example 1

Blue dye (A); A7: Mixture of compounds represented by formulas (3-1), (3-2), (3-3) and (3-4)

Resin (B): Resin B2

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)

Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

Silsesquioxane compound (H): H2; AC-SQ TA-100; Doa Synthetic

Solvent (E): E1: Propylene glycol monomethyl ether acetate

Solvent (E): E3: Propylene glycol monomethyl ether

Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Industries Co., Ltd.)

<Chemical resistance evaluation>

About the obtained coloring pattern, spectroscopy is measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y in the XYZ colorimeter of CIE using the characteristic function of the C light source) ) And the tristimulus value Y were measured.

The obtained coloring pattern was immersed in N-methylpyrrolidone for 30 minutes at 40 degreeC. After immersion, the xy chromaticity coordinates (x, y) and Y were measured in the same manner as before immersion, and the color difference ΔEab* was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Calculation method of color difference). Based on ΔEab* of the colored curable composition obtained in Comparative Example 7, the improvement rate of chemical resistance was calculated according to the following formula. Table 17 shows the results.

Improvement rate (%) = {(ΔEab* in Comparative Example 7-ΔEab* in Example) ／ ΔEab* in Comparative Example 7} × 100

Examples 37-40 and Comparative Example 8

<Preparation of colored curable resin composition>

Each component in Table 18 was mixed to obtain a colored curable resin composition. In the table, the number of resins represents the value in terms of solid content.

In addition, in Table 18, each component shows the following.

Blue dye (A); A2: Compound represented by formula (A-I-2)

Xanthene dye (X); X1: Compound represented by formula (X-1) (synthesized by a method according to the examples of JP 2013-253168 A)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)

Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

Antioxidant (G): 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f ][1,3,2] Dioxaphosphine (Sumirizu (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H2; AC-SQ TA-100; Doa Synthetic

Solvent (E): E1: Propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Industries Co., Ltd.)

<Chemical resistance evaluation>

About the obtained coloring pattern, spectroscopy is measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y in the XYZ colorimeter of CIE using the characteristic function of the C light source) ) And the tristimulus value Y were measured.

The obtained coloring pattern was immersed in N-methylpyrrolidone for 30 minutes at 40 degreeC. After immersion, the xy chromaticity coordinates (x, y) and Y were measured in the same manner as before immersion, and the color difference ΔEab* was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Calculation method of color difference). Based on ΔEab* of the colored curable composition obtained in Comparative Example 8, the improvement rate of chemical resistance was calculated according to the following formula. Table 19 shows the results.

Improvement rate (%) = {(ΔEab* in Comparative Example 8-ΔEab* in Example) ／ ΔEab* in Comparative Example 8} × 100

Provided is a colored curable resin composition capable of forming a color filter having good chemical resistance.

Claims (7)

Contains blue dye, resin, polymerizable compound, polymerization initiator and silsesquioxane compound,
The content of the silsesquioxane compound is 25 to 3000 parts by mass with respect to 100 parts by mass of the blue dye,
The colored dye is a colored curable resin composition containing a compound represented by formula (A-II).

In formula (A-II), [Y ² ] ^m- represents an arbitrary m-valent anion.
R ⁴¹ to R ⁴⁴ are each independently a hydrogen atom, a C 1 to C 20 saturated hydrocarbon group which may be substituted, or a group in which an oxygen atom is inserted between carbon atoms constituting the C 2 to C 20 alkyl group, which may be substituted. It represents an aryl group or an aralkyl group which may be substituted. R ⁴¹ and R ⁴² may combine to form a ring together with the nitrogen atom to which they are attached, or R ⁴³ and R ⁴⁴ may combine to form a ring together with the nitrogen atom to which they are attached.
In each of R ⁴⁵ to R ⁵² , an oxygen atom is inserted between carbon atoms constituting a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms, respectively. The groups may be present, or R ⁴⁶ and R ⁵⁰ may combine with each other to form -O-, -NH-, -S- or -SO ₂ -.
R ⁵³ and R ⁵⁴ are each independently a hydrogen atom, a C1-C20 saturated hydrocarbon group which may be substituted, or a group in which an oxygen atom is inserted between carbon atoms constituting the C2-C20 alkyl group, which may be substituted. It represents an aryl group or an aralkyl group which may be substituted.
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may be substituted.
X represents an oxygen atom, -NR ⁵⁷ -, or a sulfur atom.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
When the compound represented by Formula (A-II) contains a plurality of cations, the plurality of cations may have the same structure or different structures.
m represents an arbitrary natural number.] delete According to claim 1,
The blue dye is a coloring curable resin composition further comprising at least one dye selected from the group consisting of phthalocyanine dyes, anthraquinone dyes, cyanine dyes, porphyrin dyes, and thiazole dyes. According to claim 1,
The blue dye is a colored curable resin composition that is a compound having an anion having at least one element and an oxygen atom selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus. delete A color filter formed from the colored curable resin composition according to claim 1. A display device comprising the color filter according to claim 6.