JP6962862B2 - Color filter - Google Patents

Description

The present invention relates to a colored curable resin composition. More specifically, the present invention relates to a blue-colored curable resin composition.

Color filters used in display devices such as liquid crystal displays, electroluminescence display devices and plasma displays, and solid-state image sensors such as CCDs and CMOS sensors are manufactured from colored curable resin compositions. As a blue coloring curable resin composition forming a blue color filter, C.I. I. Pigment Blue 15: 6 and C.I. I. A composition containing Pigment Yellow 150 is known (Patent Document 1).

Patent Document 1 discloses that a yellow pigment is used to reduce the brightness of a blue color filter for the purpose of adjusting the white balance, and particularly for the purpose of adjusting the balance of three RGB colors.

Japanese Unexamined Patent Publication No. 2004-279617

However, in recent years, since studies have been made to expand the color gamut of display devices and the like, further improvement in saturation is required for the color filters used for them. An object of the present invention is that a color filter formed from a blue colored curable resin composition satisfies high brightness in a high saturation region.

In order to solve the above problems, it has been found that a color filter having excellent brightness in a high saturation region can be formed by including compound Y and a blue colorant as a colorant in the blue color curable resin composition, and the present invention has been achieved. ..

That is, the gist of the present invention is as follows.
[1] Contains a colorant, a resin, a polymerizable compound and a polymerization initiator.
The colorant is a colorant containing compound Y and a blue colorant.
When the spectral spectrum of the cyclohexanone solution containing the compound Y in an optical path length of 1.0 cm and 0.001% by mass of the compound Y is measured, the compound Y satisfies the following conditions 1) to 3). Sex resin composition.
Condition 1) Maximum absorption wavelength 380 nm or more and 450 nm or less Condition 2) Absorbance at maximum absorption wavelength 3 or more Condition 3) Absorbance at 460 nm 0.2 or less [2] The content of the blue colorant is 80 in 100% by mass of the colorant. The blue-colored curable resin composition according to [1], which is from mass% to 99.99 mass%.
[3] The blue coloring curable resin composition according to [1] or [2], wherein the total content of the compound Y is 0.01% by mass to 20% by mass in 100% by mass of the colorant.
[4] A color filter formed from the blue colored curable resin composition according to any one of [1] to [3].
[5] C coordinates in xy chromaticity diagram of the light source by using a characteristic function of CIE1931 colorimetric system obtained by measuring (x, y) satisfies the relationship of ^{x 2 + y 2 ≦ 0.035 [} 4] according Color filter.
[6] A display device including the color filter according to [5].

According to the present invention, it is possible to provide a blue coloring curable resin composition that can be used for forming a color filter having high brightness in a high saturation region.

The blue-colored curable resin composition of the present invention includes a colorant (hereinafter, may be referred to as a colorant (A1)), a resin (hereinafter, may be referred to as a resin (B)), and a polymerizable compound (hereinafter, may be referred to as a resin (B)). It contains a polymerizable compound (C)) and a polymerization initiator (hereinafter, may be referred to as a polymerization initiator (D)), and the colorant (A1) contains compound Y and a blue colorant. include.

The blue colorant is preferably dispersed in a solvent.
The colorant (A1) may contain a colorant other than the compound Y and the blue colorant (hereinafter, may be referred to as a colorant (A2)).
The blue colored curable resin composition of the present invention may contain a solvent (E).
The blue-colored curable resin composition of the present invention may contain a polymerization initiation aid (D1).
The blue colored curable resin composition of the present invention may further contain a leveling agent.

<Blue colorant>
The blue colorant is preferably a compound represented by the formula (AI) (hereinafter, may be referred to as a compound (AI)). Compound (AI) also includes its tautomer.

[In formula (AI),
R ^1A to R ^8A are each independently, -SO ₃ ^- represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.
R ^9A and R ^10A independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, and an aromatic hydrocarbon group or a substituent having 6 to 20 carbon atoms which may have a substituent. It represents an aralkyl group having 7 to 30 carbon atoms which may have a substituent which may be possessed by the aromatic hydrocarbon group and the aralkyl group, -SO ₃ ^- may be.
R ^11A to R ^20A are each independently, -SO ₃ ^-, represent a hydrogen atom, a saturated hydrocarbon group or a halogen atom having 1 to 10 carbon atoms.
In the above R ^{1A to} R ^20A , the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or −CO−.
R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent. aromatic hydrocarbon group substituents which may be possessed by the, -SO ₃ ^- may be.
R ⁵⁵ represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a saturated hydrocarbon group having 1 to 10 carbon atoms or a substituent, and the aromatic hydrocarbon group has. and each may be a substituent, -SO ₃ ^- may be.
In the above R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ , the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or −CO−.
^{Mr +} represents an r-valent metal ion.
k represents the number of _{SO 3} ^- groups contained in the compound represented by the formula (AI).
However, the compound represented by (AI) has at least two SO ₃ ^- groups.
r represents an integer of 2 or more. ]

The ^{saturated hydrocarbon groups represented by R 1A to} R ^20A , R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ may be linear, branched, or cyclic. Saturated hydrocarbon groups of linear or branched chains include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n. -Linear alkyl group such as decyl group; isopropyl group, sec-butyl group, tert-butyl group, isopentyl group, 1-methylpentyl group, 2-ethylbutyl group, 1-propylbutyl group, 2-ethylhexyl group and the like. Examples thereof include branched chain alkyl groups. The saturated hydrocarbon group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 6 carbon atoms.

The cyclic saturated hydrocarbon groups represented by ^{R 1A to} R ^20A , R ⁴⁵ , R ⁴⁶ , and R ^{55 may be monocyclic or polycyclic.} Examples of the cyclic alkyl group include an alicyclic saturated hydrocarbon group such as 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.

Of the saturated hydrocarbon groups represented by R ^{1A to} R ^20A , R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ , the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or -CO- (preferably an oxygen atom). Examples of the group obtained include a group represented by the following formula. In the following formula, * represents a bond.

The number of carbon atoms of the group in which the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or −CO− (preferably an oxygen atom) is preferably 1 to 10, and more preferably 1 to 6. As the saturated hydrocarbon group in which the methylene group is replaced with an oxygen atom or −CO− (preferably an oxygen atom), a linear alkyl group is preferable. When a plurality of methylene groups are substituted with oxygen atoms, the number of carbon atoms between the oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

The number of carbon atoms of the aromatic hydrocarbon group which may have a substituent represented by ^{R 9A to} R ^10A , R ⁴⁵ , R ⁴⁶ , and R ^{55 is preferably 6 to 20, more preferably 6 to 20.} It is 15, more preferably 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group, and preferably a phenyl group, a naphthyl group, a tolyl group and a xsilyl group. , More preferably a phenyl group, a naphthyl group, and even more preferably a phenyl group.

The ^{aralkyl group represented by R 9A to} R ^10A has 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a methylene group, an ethylene group and a propylene group in addition to the group described as the aromatic hydrocarbon group. Examples thereof include a group to which an alkylandyl group is bonded. The carbon number of the aralkyl group is preferably 7 to 30, more preferably 7 to 20, and even more preferably 7 to 17. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group and the like are preferable.

The substituents in the aromatic hydrocarbon group represented by R ^{9A to} R ^10A and the aralkyl group include halogen atoms such as fluorine atom, chlorine atom and iodine; alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group. ; hydroxy group; a sulfamoyl group; a methoxycarbonyl group, an alkoxycarbonyl group having 1 to 6 carbon atoms such as an ethoxycarbonyl group; methylsulfonyl alkylsulfonyl group having 1 to 6 carbon atoms such as groups -SO ₃ ^-, and the like, it is preferably ^- -SO _3. However, -SO ₃ ^-, it directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, i.e., it is preferably substituted with hydrogen atom bonded to an aromatic hydrocarbon ring.

Specific examples of the aromatic hydrocarbon group which may have a substituent represented by R ^{9A to} R ^{10A include a group represented by the following formula.} In the following formula, * represents a bond.
Specific examples of the optionally substituted aralkyl group include a group in which a methylene group is bonded to the bond of the following aromatic hydrocarbon group.

The substituent in the aromatic hydrocarbon group represented by R ⁴⁵ , R ⁴⁶ , R ⁵⁵ is a halogen atom such as a fluorine atom, a chlorine atom or iodine; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group. ; hydroxy group; a sulfamoyl group; an alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl group; alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group -SO ₃ ^-, and the like, -SO ₃ ^- Is preferable. However, -SO ₃ ^-, it directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, i.e., it is preferably substituted with hydrogen atom bonded to an aromatic hydrocarbon ring. A halogen atom is preferable as the substituent in the aromatic hydrocarbon group represented by ^{R 55.} R ⁵⁵ is preferably a phenyl group which may have a halogen atom and / or a haloalkyl group having 1 to 6 carbon atoms.
Specific examples of the aromatic hydrocarbon group which may have a substituent include a group represented by the following formula. In the following formula, * represents a bond.

Examples of the halogen atom represented by R ^{11A to} R ^20A include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

R ^1A to R ^8A are each independently, -SO ₃ ^-, is preferably a saturated hydrocarbon group a hydrogen atom or 1 to 10 carbon atoms, -SO ₃ ^-, is a hydrogen atom or a methyl group More preferably, it is a hydrogen atom or a methyl group.

Each of R ^{9A to} R ^10A independently has a saturated hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group or a substituent having 6 to 20 carbon atoms which may have a substituent. It is preferably an aralkyl group having 7 to 30 carbon atoms, and each of them independently has a saturated hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a trill group, a naphthyl group, a methylnaphthyl group; and an unsubstituted aralkyl group. A group; or one or more selected from a halogen atom, a methoxy group, an ethoxy group, a sulfamoyl group, a methylsulfonyl group, a methoxycarbonyl group, and an ethoxycarbonyl group, particularly preferably an aralkyl group substituted with one type. It is more preferable that each of them is independently a linear alkyl group having 1 to 4 carbon atoms.

From ^{the viewpoint of heat resistance and light resistance, it is preferable that at least one of R 11A to} R ^12A is a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and at least one of them is a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. It is more preferably 1 to 8 saturated hydrocarbon groups, and even more preferably at least one of them is a fluorine atom or a saturated hydrocarbon group having 1 to 4 carbon atoms.

From ^{the viewpoint of heat resistance and light resistance, it is preferable that at least one of R 13A to} R ^14A is a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and at least one of them is a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. It is more preferably 1 to 8 saturated hydrocarbon groups, and even more preferably at least one of them is a fluorine atom or a saturated hydrocarbon group having 1 to 4 carbon atoms.

From ^{the viewpoint of ease of synthesis, R 15A to} R ^20A are preferably hydrogen atoms or saturated hydrocarbon groups having 1 to 10 carbon atoms, respectively, and hydrogen atoms or saturated hydrocarbons having 1 to 4 carbon atoms. It is more preferably a hydrogen group, and even more preferably a hydrogen atom or a methyl group.

Each of R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ may be an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may independently have a saturated hydrocarbon group having 1 to 10 carbon atoms or a substituent. It is preferably an aromatic hydrocarbon group which may be substituted with a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, or a methylsulfonyl group, or a saturated hydrocarbon group having 1 to 8 carbon atoms. , A saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group represented by the following formula is more preferable. In particular, R ⁵⁵ is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms having a halogen atom, and more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms having two or more halogen atoms. preferable. The number of halogen atoms contained in the aromatic hydrocarbon group represented by R ⁵⁵ is preferably 1 to 6, more preferably 1 to 4, and even more preferably 2 to 3. The halogen atom is preferably a fluorine atom.
It is particularly preferable that R ⁵⁵ is an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bond.

^{R-valent metal ions represented by Mr +} include alkaline earth metal ions such as magnesium ion, calcium ion, strontium ion, and barium ion; titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, and cobalt ion. , Nickel ion, transition metal ion such as copper ion; typical metal ion such as zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, bismuth ion, etc., alkaline earth metal ion, transition metal ion, etc. Alternatively, typical metal ions are preferred, magnesium ions, strontium ions, barium ions, manganese ions or zinc ions are more preferred, and barium ions are even more preferred.
r is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 to 3.

In the formula (AI), ^{the number of Mr +} is the number obtained by dividing the number (k) by one less than the number (k) of _{−SO 3} ⁻ possessed by the compound represented by the formula (AI) (((AI)). It becomes k-1) / r). Therefore, the compound (AI) has a valence of 0, that is, is an electrically neutral compound.

In formula _{(A-I), -SO 3} - number of (k) is 2 or more, preferably 6 or less, more preferably 4 or less.

-SO ₃ ^- is a carbon that may be contained as any of (a) R ^{1A to} R ^8A and R ^{11A to} R ^20A , or may have a substituent represented by ^{(b) R 9A} and R ^10A. Whether it is bonded to any of the aromatic hydrocarbon groups of number 6 to 20 and the aralkyl group having 7 to 30 carbon atoms which may have a substituent represented by ^{R 9A} and R ^{10A (c).} It is bonded to any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent represented by R ⁴⁵ , R ⁴⁶ , and R ^{55, or these (a) to (c).} It is preferable that it exists as a combination of (a), (b) or (a) to (b), and it is more preferable that it exists as a combination of (a). Further, ^{among R 1A to} R ^8A and R ^{11A to} R ^20A , R ^16A and R ^19A are particularly preferable.

Wherein in (a) ~ (c), -SO 3 - is preferably bonded directly to the aromatic hydrocarbon ring of the aromatic hydrocarbon group or an aralkyl group. That -SO ₃ ^-, it is preferably substituted with hydrogen atom bonded to an aromatic hydrocarbon ring.
Two or more -SO ₃ ^- can be attached to the same aromatic hydrocarbon ring, but is preferably bonded to different aromatic hydrocarbon ring.

Examples of the compound (AI) include compounds 1 to 514 represented by the formula (AI-1) as shown in Tables 1 to 9 below. In the formula, * represents a bond.

However, the compound represented by the formula (A-I-1) is, -SO ₃ ^- and has two have a two or more hydrogen atoms of R ^h and R ^11A to R ^14A, and either the or two of -SO ₃ ^- is substituted in, preferably R ^h is a hydrogen atom, and are two that either -SO ₃ ^- is substituted, the more preferred, R ^h is hydrogen atom ^{In addition, in the benzene ring bonded to the nitrogen atom, R h} located at the para position with respect to the bonding position with the nitrogen atom is replaced with −SO ₃ ^−.

In Tables 1 to 9, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bt represents an n-butyl group, and Ph1 to Ph10 represent groups represented by the following formulas, respectively.

Among them, as a compound represented by the formula (AI),
Compounds 31 to 90, compounds 121 to 180, compounds 211 to compound 334, compounds 365 to compound 424, and compounds 455 to 514 are preferable.
More preferably, compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 271 to compound 334, compounds 380 to compound 394, and compounds 470 to 484 are more preferred.
More preferably, compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 271-compound 304, compounds 380 to compound 394, and compounds 470 to 484 are more preferred.
Compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 271 to compound 294, compounds 380 to compound 394, and compounds 470 to 484 are even more preferred.
Compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 279 to 294, compounds 380 to 394, and compounds 470 to 484 are particularly preferred.

The compound (AI) is prepared, for example, by sulfonated a salt represented by the formula (Ay) to obtain a salt represented by the formula (Ax), and further, an acetate of ^{an r-valent metal ion Mr +.} It can be produced by reacting with salts, carbonates, phosphates, sulfates, silicates, cyanides or halides (preferably chlorides).

[In the formula (Ay),
R ^{1B to} R ^8B each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.
R ^9B and R ^10B independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, and an aromatic hydrocarbon group or a substituent having 6 to 20 carbon atoms which may have a substituent. a represents an even aralkyl group having 7 to 30 carbon atoms have, aromatic hydrocarbon group and the aralkyl group, -SO ₃ ^- as a substituent having no.
R ^{11B to} R ^20B independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.
In the above R ^{1B to} R ^20B , the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or −CO−.
R ^45B and R ^46B each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. aromatic hydrocarbon group, -SO ₃ ^- as a substituent having no.
R ^55B represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the aromatic hydrocarbon group is substituted. It does not have a ^- -SO ₃ as the base.
In the above R ^45B , R ^46B , and R ^55B , the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or −CO−.
A _B ^j- represents an anion of arbitrary j valence.
j represents an integer of 1 or more and 5 or less. ]

A _B ^j- as, for example, chloride ion, phosphate ion, sulfate ion, benzenesulfonate ion, naphthalenesulfonate ion, perchlorate ion, BF ₄ ^-, PF ₆ ^-, and the like.

[In formula (AX ^{), R 1A to R 20A} , R ⁴⁵ , R ⁴⁶ , R ⁵⁵ , and k are synonymous with the above.
A _A ^{z +} represents an arbitrary z-valent cation. z represents an integer of 1 or more and 5 or less. ]
A _A ^{z +} is preferably hydron.

Various known methods for sulfonation, such as Journal of Organic Chemistry, (1994), vol. 59, # 11, p. The method described in 3232-3236 can be mentioned.

The other blue colorant may be a conventionally known one, but may be either a dye or a pigment, or may be a mixture of a pigment and a dye. Above all, it is preferable to use a pigment from the viewpoint of heat resistance and lightness.

Specific examples of the blue pigment include compounds classified as Pigments in the Color Index (The Society of Dyers and Colorists Publishing) and compounds described in JP-A-2017-16100.
Specifically, for example, C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; and the like. Above all, C.I. I. It preferably contains Pigment Blue 15: 6. Further, as a purple pigment, for example, C.I. I. Pigment Violet 19, 23 may be contained.

Examples of the dye include compounds classified into acid dyes, direct dyes, basic dyes, disperse dyes, and oil-soluble dyes according to the Color Index (published by The Society of Dyers and Colorists). for example,
Acid Alizarin Violet N;
C. I. Acid Black 1,2,24,48;
Acid Blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324: 1, 335,340;
Acid Chromium Violet K;
Acid fuchsin;
C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 57,77,80,81,84,85,86,90,93,94,95,97,98,99,100,101,106,107,108,109,113,114,115,117, 119,137,149,150,153,155,156,158,159,160,161,162,163,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293; or derivatives of these dyes.

From the viewpoint of high saturation, the content of the blue colorant is preferably 80 to 99.99% by mass, more preferably 85% by mass or more, and 90% by mass, based on 100% by mass of the solid content of the colorant. It is more preferably% or more.

The blue colorant may be treated with rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound, or a sulfuric acid atomization method, if necessary. A micronization treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method for ionic impurities, or the like may be performed.

The blue colorant becomes a blue colorant dispersion liquid in a state of being uniformly dispersed in the solution by carrying out the dispersion treatment by containing the dispersant.

Examples of the dispersant include surfactants, which may be cationic, anionic, nonionic, or amphoteric surfactants. Specific examples thereof include polyester-based, polyamine-based, and acrylic-based dispersants. These dispersants may be used alone or in combination of two or more. Dispersants are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (BASF). (Manufactured by), Ajispar (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie), and the like. As the dispersant, the resin (B) described later may be used.
When a dispersant is used, the amount used is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the blue colorant. When the amount of the dispersant used is in the above range, a dispersion liquid in a uniformly dispersed state tends to be obtained.

The content of the blue colorant is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and preferably 3 to 20% by mass in 100% by mass of the blue colorant dispersion liquid. More preferred. When two or more kinds of blue colorants are used, they may be mixed as a dispersion liquid at the time of use.

The content of the blue colorant is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, and 1 to 20% by mass in 100% by mass of the blue coloring curable resin composition. It is more preferably mass%.

<Compound Y>
Compound Y is a compound that satisfies the following conditions 1) to 3) when the spectral spectrum of a cyclohexanone solution containing 0.001% by mass of the compound Y is measured with an optical path length of 1.0 cm.
Condition 1) Maximum absorption wavelength 380 nm or more and 450 nm or less Condition 2) Absorbance at maximum absorption wavelength 3 or more Condition 3) Absorbance at 460 nm 0.2 or less The maximum absorption wavelength and absorbance of compound Y are cyclohexanone containing 0.001% by mass of compound Y. A solution can be prepared, and then the solution can be measured by, for example, placing it in a measuring container (for example, a cuvette) having an optical path length of 1.0 cm and using an ultraviolet-visible-near-infrared spectrophotometer. Absorbance is expressed as a relative value with cyclohexanone as a blank.

The maximum absorption wavelength of compound Y is 380 nm or more and 450 m or less, preferably 385 nm or more, more preferably 390 nm or more, further preferably 395 nm or more, and preferably 445 nm or less, more preferably. It is 440 nm or less. The compound Y satisfying the above conditions can improve the brightness in combination with the blue colorant.

The absorbance of compound Y at the maximum absorption wavelength is 3 or more, preferably 3.2 or more, more preferably 3.4 or more, still more preferably 3.6 or more, and even more preferably 3. 8 or more.

The absorbance of compound Y at 460 nm is 0.2 or less, preferably 0.18 or less, more preferably 0.16 or less, still more preferably 0.14 or less, and even more preferably 0. It is 12 or less.

The thermal decomposition temperature of compound Y may be, for example, 100 ° C. to 460 ° C., 120 ° C. to 440 ° C., 140 ° C. to 420 ° C., 160 ° C. to 400 ° C., or 180 ° C. to 380 ° C.

Compound Y is preferably a porphyrin compound, a merocyanine compound, or a methine compound, and more preferably a porphyrin compound.
The porphyrin compound may have an aromatic ring group or a heterocyclic group which may have a substituent bonded to the porphyrin ring. Examples of the aromatic ring group include a phenyl group, a naphthyl group, a tolyl group and a xsilyl group, and a phenyl group is preferable. Examples of the heterocyclic group include a pyridine group, a pyrazine group, a pyrimidine group and the like. The substituent may be an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a carboxyl group or the like. When an aromatic ring group or a heterocyclic group which may have a substituent is bonded, the number of groups to be bonded is preferably 1 to 8, more preferably 2 to 4, and even more preferably 4. When a plurality of aromatic ring groups or heterocyclic groups which may have substituents are bonded, they may be the same, may be different, and are preferably the same.
The porphyrin compound may or may not form a complex. When the porphyrin compound forms a complex, it is preferable that Cu, Pd, Co, Ni, Fe, or Zn are coordinated to form a complex, and Cu is coordinated to form a complex. More preferred. The porphyrin compound does not contain the tetraazaporphyrin compound.
As the porphyrin compound, for example, visible light absorbing material (Yamada Chemical Co., Ltd. FDB-002), 5,10,15,20-tetraphenyl-21H, 23H-porfin copper (II), tetraphenylporphyrin and the like can be obtained. Is.

Compound Y may contain one kind or two or more kinds.
The total content of compound Y is preferably 0.01 to 20% by mass, more preferably 15% by mass or less, and further preferably 10% by mass or less in 100% by mass of the colorant.

The total content of the compound Y is preferably 0.001 to 20% by mass, more preferably 0.005 to 15% by mass, and 0.01 in 100% by mass of the blue colored curable resin composition. It is more preferably 10% by mass.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (a) (hereinafter, "(a)"). A resin having a structural unit derived from) is more preferable. The resin (B) is a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”). Structural units derived from the monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)"), and side. It is preferable to have at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the chain.

Specifically, as (a), for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, oxalic acid mono [2- (meth). ) Acryloyloxyethyl] and the like, preferably acrylic acid, methacrylic acid, maleic anhydride.

In (b), a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and a (meth) acryloyloxy group is preferable. ..
In addition, in this specification, "(meth) acrylic acid" represents at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meta) acryloyl" and "(meta) acrylate" have the same meaning.
Examples of (b) include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate 3-ethyl-3-(. Examples thereof include acryloyloxymethyloxetanetetrahydrofurfuryl (meth) acrylate, preferably glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth). Acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane.

Examples of (c) include methyl (meth) acrylate, butyl (meth) acrylate cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decane-8. -Il (meth) acrylate benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like, preferably styrene and vinyl. Toluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferable.

The resin having a structural unit having an ethylenically unsaturated bond in the side chain is obtained by adding (b) to the copolymer of (a) and (c) or by adding (b) to the copolymer of (b) and (c). It can be manufactured by adding (a) to. The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. ..
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 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and even more preferably 70 to 135 mg-KOH / g in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide 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 further preferably 17 to 55% by mass with respect to the total amount of solids.

<Colorant (A2)>
The blue color-curable resin composition of the present invention may contain a dye (A2-1) other than the colorant (A1) and a pigment (A2-2) as the colorant (A2).

The dye (A2-1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye include compounds classified by the Color Index (The Society of Dyers and Colorists) as having a hue other than pigments, and known dyes described in dyeing notes (Color Dyeing Co., Ltd.). Be done. According to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acrydin dye, styryl dye, coumarin. Examples include dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred. Further, as the dye, those described in JP-A-2015-28121, JP-A-2013-7032, JP-A-2013-144724, JP-A-2013-53292 and the like may be used.

As the pigment (A2-2), a known pigment can be used without particular limitation, and examples thereof include pigments classified as pigments by the Color Index (The Society of Dyers and Colorists Publishing).
Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
And so on.

The content of the colorant (A2) is preferably 0.1 to 60% by mass, more preferably 0.5 to 55% by mass, still more preferably 1 to 50% by mass, based on the total amount of solids. %.
Here, the "total amount of solids" in the present specification means an amount obtained by subtracting the solvent content from the total amount of the blue colored curable resin composition. The total amount of solids and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, which is preferable. Is a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa ( Meta) acrylate and the like can be mentioned.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass, based on the total amount of solids. be.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. by the action of light or heat, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl). ) Octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine 2-methyl-2-morpholino-1- (4) -Methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one, 1-hydroxycyclohexylphenylketone 2,4-bis (trichloromethyl)- 6-Piperonyl-1,3,5-triazine 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, etc. Can be mentioned.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

The blue-colored curable resin composition of the present invention may contain a polymerization initiation aid.

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiator (D1) include 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, and 2,4-diethylthioxanthone. Examples thereof include N-phenylglycine.

When these polymerization initiators (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

The blue colored curable resin composition of the present invention preferably contains a solvent.

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent in the molecule). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Examples of the solvent include ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone (intramolecular). Solvents containing -COO- and not -O-; ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether ( Solvent containing -O- in the molecule and not -COO-);
Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (intramolecular-COO- Solvent containing -O-);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, cyclohexanone (solvents containing -CO- and not -COO- in the molecule); butanol, cyclohexanol , Alcohol solvent such as propylene glycol (solvent containing OH in the molecule and not containing -O-, -CO- and -COO-); and the like. Examples thereof include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone and ethyl 3-ethoxypropionate are more preferable.

When the solvent (E) is contained, 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 blue colored curable resin composition of the present invention. %. In other words, the total solid content of the blue 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 within the above range, the flatness at the time of coating is good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed. ..

<Other ingredients>
The blue-colored curable resin composition of the present invention may be used in the technical fields such as leveling agents, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like, if necessary. It may contain known additives.

<Manufacturing method of blue colored curable resin composition>
The blue-colored curable resin composition of the present invention contains a colorant (A1), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E) and other components as necessary. It can be prepared by mixing.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the blue colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Above all, the photolithography method is preferable.

In the color filter of the present invention, the coordinates (x, y) in the xy chromaticity diagram in the CIE 1931 color system measured by using the characteristic function of the C light source satisfy the relationship of ^{x 2} + y ^{2 ≤ 0.035.} Preferably, ^{it is more preferable to satisfy the relationship of x 2} + y ² ≤ 0.030, and the coordinates (x, y) in the xy chromaticity diagram in the CIE 1931 color system are (0.120, 0.080), (0. The range enclosed by 120, 0.105), (0.136, 0.080) and (0.136, 0.105) is more preferable.

When the blue coloring curable resin composition contains the blue coloring agent and the compound Y as the coloring agent, it is possible to produce a color filter having excellent brightness particularly in the high saturation region. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can be adapted to the gist of the above and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.

[Synthesis Example 1]
The following reaction was carried out in a nitrogen atmosphere. 50 parts of the compound represented by the formula (CI-2) and 188 parts of N, N-dimethylformamide were put into a flask equipped with a cooling tube and a stirring device, and the mixture was stirred for 30 minutes while cooling in an ice bath. 40 parts of potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into the flask, and the mixture was further stirred for 1 hour while cooling in an ice bath. While the reaction solution was ice-cooled, 55.6 parts of iodidetan (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise.
The reaction solution was heated to 35 ° C. using an oil bath, stirred for 5 hours, and then allowed to cool to room temperature. 1000 parts of a 10% sodium chloride aqueous solution was put into another flask equipped with a stirrer, and the reaction solution was added dropwise while stirring. After stirring for 30 minutes, the mixture was filtered to obtain a solid. The obtained solid was washed 3 times with 500 parts of ion-exchanged water and dried at 60 ° C. under reduced pressure to obtain 53.0 parts of the compound represented by the formula (CI-3). Yield 93.5%.

The following reaction was carried out in a nitrogen atmosphere. After putting 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile into a flask equipped with a cooling tube and a stirrer, the mixture was stirred at room temperature for 30 minutes. After dropping 40.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) into the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. After dropping 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) into the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. An aqueous solution prepared by dissolving 79.2 parts of monochloroacetate in 120 parts of ion-exchanged water was added to the flask, 60.4 parts of a 30% sodium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 18 hours. After adding 600 parts of ion-exchanged water to the flask, the mixture was stirred for 1 hour, and the precipitated yellowish white solid was collected by filtration. The obtained yellowish white solid was washed with 120 parts of acetonitrile and then with 560 parts of ion-exchanged water. The washed yellow-white solid, 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 156 parts of toluene were put into a flask equipped with a stirrer, and the mixture was charged at room temperature for 2 hours. Stirred. 80.8 parts of a 30% aqueous sodium hydroxide solution was added dropwise thereto over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by a liquid separation operation. After adding 156 parts of ion-exchanged water to the obtained organic layer for liquid separation washing, 156 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added for liquid separation washing. The obtained organic layer was concentrated with an evaporator and then dried under reduced pressure at 35 ° C. to obtain a compound represented by the formula (BI-3) as a white solid. The yield was 43.4 parts and the yield was 58.0%.

The following reaction was carried out in a nitrogen atmosphere. 13.2 parts of the compound represented by the formula (BI-3), 19.0 parts of the compound represented by the formula (CI-3) and 38 parts of toluene are placed in a flask equipped with a cooling tube and a stirrer. Then, 9.2 parts of phosphorus oxychloride was added, and the mixture was stirred at 100 ° C. for 7 hours. The reaction mixture was then cooled to room temperature and then diluted with 29 parts of methyl ethyl ketone. Next, a mixed solution of 114 parts of ion-exchanged water and 10 parts of a 35% hydrochloric acid aqueous solution was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was solvent-distilled off with an evaporator and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (X-II-7) as a bluish-purple solid. The yield of the bluish-purple solid was 39.4 parts.

The following reaction was carried out in a nitrogen atmosphere. 38.4 parts of the compound represented by the formula (X-II-7) and 112 parts of methylene chloride were put into a flask equipped with a cooling tube and a stirrer, and the mixture was stirred for 30 minutes. While the reaction solution was ice-cooled and the internal temperature was maintained at 10 ° C., 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and then the reaction solution was heated to room temperature and stirred for 9 hours. Then, the reaction solution was ice-cooled and diluted with a mixed solution of 64 parts of N, N-dimethylformamide and 4.9 parts of ion-exchanged water while keeping the internal temperature at 10 ° C. The diluted reaction solution was poured into 1120 parts of toluene and then stirred for 30 minutes to precipitate a viscous solid. After the oil layer was discharged by decantation, 320 parts of toluene was added to the obtained viscous solid and stirred for 30 minutes. 832 parts of 20% saline solution was added to the viscous solid obtained by discharging the oil layer by decantation, and the mixture was stirred for 1 hour, and then the blue solid was collected by filtration. The obtained blue solid was washed with 576 parts of 20% brine and dried under reduced pressure at 35 ° C. The solid and 128 parts of methanol were put into a flask equipped with a stirrer, stirred for 30 minutes, filtered, and separated into a solid and a filtrate. This filtrate is referred to as filtrate A3. The solid collected by filtration was washed with 192 parts of methanol and separated into a solid and a filtrate by filtration. This filtrate is referred to as filtrate B3. After mixing the filtrate A3 and the filtrate B3 and removing the solvent with an evaporator, the mixture was dried under reduced pressure at 40 ° C. to obtain a compound represented by the formula (XI-7) as a bluish-purple solid. The yield of the bluish-purple solid was 38.3 parts.

To a flask equipped with a cooling tube and a stirrer, add 28.0 parts of the compound represented by the formula (XI-7), 43.2 parts of barium chloride dihydrate and 356 parts of ion-exchanged water, and bring the temperature to 40 ° C. After stirring for 2 hours, the reaction suspension was filtered. The solid collected by filtration and 350 parts of ion-exchanged water were put into a flask equipped with a stirrer and stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 280 parts of ion-exchanged water and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (AI-7) as a bluish-purple solid. The yield was 24.5 parts and the yield was 81.7%.

Identification of the compound represented by the formula (AI-7) (mass spectrometry) Ionization mode = ESI-: m / z = 949.5 [M-Ba + 2H] ^-
Exact Mass [M-Ba]: 947.28

[Synthesis Example 2] Resin (B-1)
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 85 ° C. with stirring. Then 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] deca-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 25 parts of a mixture of deca-9-ylacrylate (content ratio 1: 1), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. bottom. On the other hand, a mixed solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropping, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a B-type viscosity (23 ° C.) of 23 mPas and a solid content of 25.6%. .. The weight average molecular weight Mw of the produced copolymer was 8000, the solid acid value was 111 mg-KOH / g, and the dispersity was 2.1. The resin (B-1) has the following structural units.

[Preparation of dispersion liquid 1]
8.2 parts of compound (AI-7), 6.1 parts of dispersant BYKLPN-6919 (solid content equivalent), 2.1 parts of resin (B-1) (solid content equivalent) as resin, propylene After weighing 84 parts of glycol monomethyl ether acetate, 600 parts of 0.4 μm zirconia beads are added, and the mixture is shaken for 1 hour using a paint conditioner (manufactured by LAU), and then the zirconia beads are removed by filtration to obtain the dispersion liquid 1. Made.

[Preparation of dispersion liquid 2]
C. I. Pigment Blue 15: 6 (pigment) 10 parts, acrylic pigment dispersant (solid content equivalent) 3.5 parts, resin (B-1) (solid content equivalent) 4 parts, propylene glycol monomethyl ether acetate 80 parts and 2.6 parts of ethyl lactate were mixed, and the pigment was sufficiently dispersed using a bead mill to prepare a dispersion liquid 2.

[Preparation of dispersion liquid 3]
C. I. Pigment Yellow 150 (pigment) 13 parts, acrylic pigment dispersant (solid content equivalent) 3.9 parts, resin (B-1) (solid content equivalent) 6.1 parts, propylene glycol monomethyl ether acetate 77 parts were mixed, and the pigment was sufficiently dispersed using a bead mill to prepare a dispersion liquid 3.

<Preparation of blue colored curable resin composition>
[Example 1]
A blue colored curable resin composition was obtained by mixing the following components.
Blue colorant: Dispersion 1 454 parts Blue colorant: Dispersion 2 192 parts Compound Y: Y-1: Porphyrin compound (FDB-002 (thermal decomposition temperature 340 ° C.); manufactured by Yamada Chemical Industry Co., Ltd.) 0.33 Partial resin (B): Resin (B-1) (in terms of solid content) 33 parts polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts polymerization Initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure® OXE01; BASF; O-acyloxime compound) 8.0 Part Solvent (E): Cyclohexanone 146 Part Solvent (E): Propropylene Glycol Monomethyl Ether Acetate 759 Part Solvent (E): Ethyl Lactate 19 Part Leveling Agent (H): Polyether Modified Silicone Oil (Solid Content Conversion) (Torre Silicone SH8400) ; Made by Toray Dow Corning Co., Ltd. 0.16 copies

<Preparation of blue colored curable resin composition>
[Example 2]
Instead of using 0.33 parts of Y-1, 0.8 parts of 5,10,15,20-tetraphenyl-21H, 23H-porfin copper (II) (manufactured by Aldrich: hereinafter referred to as Y-2) is used. A blue colored curable resin composition was obtained in the same manner as in Example 1 except that it was used.

<Measurement of spectral spectrum of compound Y>
Compound Y was dissolved in cyclohexanone so that the concentration was 0.001% by mass to obtain a solution. The spectral spectrum of the cyclohexanone single solution as the solution and the blank was measured using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation; 1.0 cm square quartz cell). The results are shown in Table 10.

<Making a coloring pattern>
A blue colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After allowing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to create an air atmosphere of 60 mJ / cm. Light was irradiated with an exposure amount of ^{2 (based on 365 nm).} As the photomask, a photomask having a 100 μm line-and-space pattern formed was used. The colored composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and then in an oven at 230. Post-baking was performed at ° C. for 20 minutes to obtain a colored pattern.

<Film thickness measurement>
The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 11.

<Saturation evaluation>
The obtained coloring pattern was spectrally measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x) in the CIE 1931 color system were used using the characteristic function of the C light source. , Y) and the stimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 11.

<Preparation of blue colored curable resin composition>
[Example 3]
A blue colored curable resin composition was obtained by mixing the following components.
Blue colorant: Dispersion liquid 1 258 parts Blue colorant: Dispersion liquid 2 126 parts Compound Y: Y-1: Porphyrin compound (FDB-002; manufactured by Yamada Chemical Co., Ltd.)
0.24 parts Resin (B): Resin (B-1) (solid content equivalent) 40 parts polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50-part polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF; O-acyloxime compound) 8.0 parts Solvent (E): Cyclohexanone 119 parts Solvent (E): propylene glycol Monomethyl ether acetate 728 parts Solvent (E): Ethyl lactate 23 parts Leveling agent (H): Polyether-modified silicone oil (solid content equivalent) ( Torre Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd. 0.13 copies

<Preparation of blue colored curable resin composition>
[Example 4]
A blue colored curable resin composition was obtained by mixing the following components.
Blue Colorant: Dispersion 1 241 parts Blue Colorant: Dispersion 2 140 parts Compound Y: Y-2: 5,10,15,20-Tetraphenyl-21H, 23H-Polfin Copper (II) (manufactured by Aldrich) 0.76 parts Resin (B): Resin (B-1) (solid content equivalent) 39 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF; O-acyloxime compound) 8.0 parts solvent (E): cyclohexanone 119 parts solvent (E): propylene glycol monomethyl ether acetate 731 parts solvent (E): ethyl lactate 23 parts leveling agent (H): polyether-modified silicone oil (solid content equivalent) ( Torre Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd. 0.13 copies

<Preparation of blue colored curable resin composition>
[Comparative Example 1]
A blue colored curable resin composition was obtained by mixing the following components.
Blue colorant: Dispersion 1 175 parts Blue colorant: Dispersion 2 379 parts Dispersion 3 11.6 parts Resin (B): Resin (B-1) (solid content equivalent) 31 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD® DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one- 2-Imin (Irgacure (registered trademark) OXE01; manufactured by BASF; O-acyloxime compound) 8.0 parts solvent (E): cyclohexanone 119 parts solvent (E): propylene glycol monomethyl ether acetate 761 parts solvent (E): Ethyl lactate 18 parts Leveling agent (H): Polyether-modified silicone oil (solid content equivalent) (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts

<Making a coloring pattern>
A blue colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After allowing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to create an air atmosphere of 60 mJ / cm. Light was irradiated with an exposure amount of ^{2 (based on 365 nm).} As the photomask, a photomask having a 100 μm line-and-space pattern formed was used. The colored composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and then in an oven at 230. Post-baking was performed at ° C. for 20 minutes to obtain a colored pattern.

<Film thickness measurement>
The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 12.

<Saturation evaluation>
The obtained coloring pattern was spectrally measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x) in the CIE 1931 color system were used using the characteristic function of the C light source. , Y) and the stimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 12.

<Preparation of blue colored curable resin composition>
[Example 5]
A blue colored curable resin composition was obtained by mixing the following components.
Blue colorant: Dispersion 1 285 parts Blue colorant: Dispersion 2 190 parts Compound Y: Y-3: Tetraphenyl porphyrin (Cas No. 917-23-7, manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.73 parts Resin (B): Resin (B-1) (solid content equivalent) 48 parts polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 61 parts polymerization started Agent (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF; O-acyloxime compound) 10 parts solvent ( E): Cyclohexanone 146 parts Solvent (E): Propropylene glycol monomethyl ether acetate 876 parts Solvent (E): Ethyl lactate 28 parts Leveling agent (H): Polyether-modified silicone oil (solid content equivalent) (Torre Silicone SH8400; Toredau Made by Corning Co., Ltd. 0.16 copies

<Measurement of spectral spectrum of compound Y-3>
Compound Y-3: (Tetraphenylporphyrin (Cas No. 917-23-7, manufactured by Tokyo Chemical Industry Co., Ltd.)) was dissolved in cyclohexanone so that the concentration was 0.001% by mass to obtain a solution. .. The spectral spectrum of the cyclohexanone single solution as the solution and the blank was measured using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation; 1.0 cm square quartz cell). The results are shown in Table 13.

<Making a coloring pattern>
A blue colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After allowing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to create an air atmosphere of 60 mJ / cm. Light was irradiated with an exposure amount of ^{2 (based on 365 nm).} As the photomask, a photomask having a 100 μm line-and-space pattern formed was used. The colored composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and then in an oven at 230. Post-baking was performed at ° C. for 20 minutes to obtain a colored pattern.

<Film thickness measurement>
The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 14.

<Saturation evaluation>
The obtained coloring pattern was spectrally measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x) in the CIE 1931 color system were used using the characteristic function of the C light source. , Y) and the stimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 14.

Claims (4)

Contains colorants, resins, polymerizable compounds and polymerization initiators
The colorant is a colorant containing compound Y and a blue colorant.
The compound Y is characterized by being a porphyrin compound satisfying the following conditions 1) to 3) when the spectral spectrum of a cyclohexanone solution containing the compound Y in an amount of 0.001% by mass is measured with an optical path length of 1.0 cm. A color filter formed from a blue-colored curable resin composition.
The coordinates (x, y) in the xy chromaticity diagram in the CIE1931 color system measured using the characteristic function of the C light source are (0.120, 0.080), (0.120, 0.105), ( A color filter that satisfies the range enclosed by (0.136, 0.080) and (0.136, 0.105) .
Condition 1) Maximum absorption wavelength 380 nm or more and 450 nm or less Condition 2) Absorbance at maximum absorption wavelength 3 or more Condition 3) Absorbance at 460 nm 0.2 or less The color filter according to claim 1, wherein the content of the blue colorant is 80% by mass to 99.99% by mass in 100% by mass of the colorant. The color filter according to claim 1 or 2, wherein the total content of compound Y is 0.01% by mass to 20% by mass in 100% by mass of the colorant. A display device including the color filter according to any one of claims 1 to 3.