KR102385559B1 - Blue colored curable resin composition, color filter and display device - Google Patents

Abstract

This invention makes it a subject that the color filter and display device formed from blue coloring curable resin composition satisfy the high brightness in a high chroma area|region.
A cyclo containing a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant is a colorant comprising a compound Y and a blue colorant, wherein the compound Y is an optical path length of 1.0 cm and contains 0.001% by mass of the compound Y When the spectral spectrum of a hexanone solution is measured, the following conditions 1) - 3) are satisfy|filled, The blue coloring curable resin composition characterized by the above-mentioned.
Condition 1) Maximum absorption wavelength 380 nm or more and 450 nm or less
Condition 2) Absorbance 3 or more at maximum absorption wavelength
Condition 3) Absorbance 0.2 or less at 460 nm

Description

Blue colored curable resin composition, a color filter, and a display device TECHNICAL FIELD

The present invention relates to a colored curable resin composition. In detail, it is related with blue coloring curable resin composition.

The color filter used for display apparatuses, such as a liquid crystal display device, an electroluminescent display device, and a plasma display, and solid-state imaging elements, such as a CCD and CMOS sensor, is manufactured from a colored curable resin composition. As a blue colored curable resin composition which forms a blue color filter, as a coloring agent, C.I. Pigment Blue 15:6 and C.I. A composition containing Pigment Yellow 150 is known (Patent Document 1).

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

Japanese Laid-Open Patent Publication No. 2004-279617

However, in recent years, since studies to expand the color gamut have been conducted in display devices and the like, further improvement in chroma is required for color filters used for them. This invention makes it a subject that the color filter formed from blue coloring curable resin composition satisfy|fills the high brightness in a high chroma area|region.

In order to solve the said subject, when blue coloring curable resin composition contains the compound Y and a blue coloring agent as a coloring agent, it discovered that the color filter excellent in the brightness in a high chroma area|region could be formed, and it led to this invention.

That is, the summary of this invention is as follows.

[1] A colorant, a resin, a polymerizable compound, and a polymerization initiator are included,

The colorant is a colorant comprising compound Y and a blue colorant,

Blue coloring, characterized in that the compound Y satisfies the following conditions 1) to 3) when the spectral spectrum of a cyclohexanone solution containing 0.001 mass % of the compound Y is measured with an optical path length of 1.0 cm. Curable resin composition.

Condition 1) Maximum absorption wavelength 380 nm or more and 450 nm or less

Condition 2) Absorbance 3 or more at maximum absorption wavelength

Condition 3) Absorbance 0.2 or less at 460 nm

[2] Blue coloring curable resin composition as described in [1] whose content rate of the said blue coloring agent is 80 mass % - 99.99 mass % in 100 mass % of coloring agents.

[3] The blue colored 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 [1] or [2].

[5] The color filter according to [4], wherein the coordinates (x, y) in the xy chromaticity diagram in the CIE1931 color space measured using the characteristic function of the C light source satisfy the relationship of x ² +y ² ≤ 0.035. .

[6] A display device comprising the color filter according to [5].

ADVANTAGE OF THE INVENTION According to this invention, the blue coloring curable resin composition which can be used for formation of the color filter with high brightness in a high chroma area can be provided.

The blue coloring curable resin composition of this invention is a coloring agent (Hereinafter, it may call a coloring agent (A1).), resin (Hereinafter, it may call resin (B).), a polymeric compound (Hereinafter, it may call it polymeric.) The compound (C) may be referred to.) and a polymerization initiator (hereinafter, may be referred to as a polymerization initiator (D).) are included, and the colorant (A1) contains the compound Y and a blue colorant.

It is preferable that the blue coloring agent is disperse|distributed to the solvent.

The coloring agent (A1) may contain the coloring agent (Hereinafter, it may be called coloring agent (A2)) other than the compound Y and a blue coloring agent.

The blue colored curable resin composition of this invention may contain the solvent (E).

The blue coloring curable resin composition of this invention may contain the polymerization initiation adjuvant (D1).

The blue coloring curable resin composition of this invention may contain the leveling agent further.

<Blue colorant>

It is preferable that a blue coloring agent is a compound (Hereinafter, it may be called compound (AI)) represented by a formula (AI). Compound (AI) includes its tautomer.

(Formula 1)

[in formula (A-I),

R ^1A to R ^8A each independently represent —SO ₃ ^— , a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms,

R ^9A and R ^10A are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent and the substituent that the aromatic hydrocarbon group and the aralkyl group may have may be -SO ₃ ^- ,

R ^11A to R ^20A each independently represent —SO ₃ ^— , a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom,

In R ^1A to R ^20A , the methylene group included 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, and the substituent which the aromatic hydrocarbon group may have is -SO ₃ ^- can be,

R ⁵⁵ 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 substituent which the aromatic hydrocarbon group may have may be —SO ₃ ^— ,

In R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ , the methylene group included in the saturated hydrocarbon group may be substituted with an oxygen atom or —CO—,

M ^r+ represents an r-valent metal ion,

k represents the number of SO ₃ ⁻ groups 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 group represented by R ^1A to R ^20A , R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ may be linear, branched or cyclic. Examples of the linear or branched saturated hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, etc. A linear alkyl group; Branched alkyl groups, such as an isopropyl group, sec-butyl group, tert-butyl group, isopentyl group, 1-methylpentyl group, 2-ethylbutyl group, 1-propylbutyl group, and 2-ethylhexyl group and the like. Carbon number of the said saturated hydrocarbon group is 1-10, More preferably, it is 1-8, More preferably, it is 1-6.

The cyclic saturated hydrocarbon group represented by R ^1A to R ^20A , R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ may be monocyclic or polycyclic. As said cyclic alkyl group, alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group, are mentioned. Carbon number of the said cyclic saturated hydrocarbon group becomes like this. Preferably it is 3-10, More preferably, it is 6-10.

Among the saturated hydrocarbon groups represented by R ^1A to R ^20A , R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ , examples of the group in which a methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom or -CO- (preferably an oxygen atom) include, For example, the group represented by the following formula is mentioned. In the following formula, * represents a bond.

(Formula 2)

1-10 are preferable and, as for carbon number of the group by which the methylene group contained in the said saturated hydrocarbon group was substituted by the oxygen atom or -CO- (preferably oxygen atom), 1-6 are more preferable. As the saturated hydrocarbon group in which the methylene group is substituted with an oxygen atom or -CO- (preferably an oxygen atom), a linear alkyl group is preferable. When several methylene groups are substituted with an oxygen atom, 1-4 are preferable and, as for carbon number between oxygen atoms, 2-3 are more preferable.

The number of carbon atoms of the optionally substituted aromatic hydrocarbon group represented by R ^9A to R ^10A , R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ is preferably 6 to 20, more preferably 6 to 15, still more preferably 6 -12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, preferably a phenyl group, a naphthyl group, a tolyl group, and a xylyl group, More preferably, they are a phenyl group and a naphthyl group, More preferably, they are a phenyl group.

Examples of the aralkyl group represented by R ^9A to R ^10A include a group in which an alkanediyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methylene group, ethylene group, or propylene group, is bonded to the group described as the aromatic hydrocarbon group. can be heard Carbon number of the said aralkyl group becomes like this. Preferably it is 7-30, More preferably, it is 7-20, More preferably, it is 7-17. As said aromatic hydrocarbon group, a phenyl group, a naphthyl group, etc. are preferable.

Examples of the substituent in the aromatic hydrocarbon group and the aralkyl group represented by R ^9A to R ^10A include a halogen atom such as a fluorine atom, a chlorine atom and an iodine; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; A sulfamoyl group; A C1-C6 alkylsulfonyl group, such as a methylsulfonyl group; A C1-C6 alkoxycarbonyl group, such as a methoxycarbonyl group and an ethoxycarbonyl group; -SO ₃ ^- , etc. are mentioned, -SO ₃ ^- is preferable. However, it is preferable that -SO ₃ ^- is directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, the hydrogen atom bonded to the aromatic hydrocarbon ring is substituted.

Specific examples of the optionally substituted aromatic hydrocarbon group 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 bonding hand of the aromatic hydrocarbon group shown below.

(Formula 3)

(Formula 4)

Examples of the substituent in the aromatic hydrocarbon group represented by R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ include a halogen atom such as a fluorine atom, a chlorine atom and an iodine; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; A pamoyl group; A C1-C6 alkylsulfonyl group, such as a methylsulfonyl group; A C1-C6 alkoxycarbonyl group, such as a methoxycarbonyl group; -SO ₃ ^- etc. are mentioned, -SO ₃ ^- is preferable. . However, it is preferable that -SO ₃ ^- is directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, the hydrogen atom bonded to the aromatic hydrocarbon ring is substituted. As the substituent in the aromatic hydrocarbon group represented by R ⁵⁵ , a halogen atom is preferable. R ⁵⁵ is preferably a halogen atom and/or a phenyl group which may have a haloalkyl group having 1 to 6 carbon atoms.

As a specific example of the aromatic hydrocarbon group which may have a substituent, the group represented by a following formula is mentioned. In the following formula, * represents a bond.

(Formula 5)

(Formula 6)

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

R ^1A to R ^8A are each independently —SO ₃ ^— , a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably —SO ₃ ^— , a hydrogen atom or a methyl group, a hydrogen atom or a methyl group It is more preferable that

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

In terms of heat resistance and light resistance, at least one of R ^11A to R ^12A is preferably a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and more preferably at least either one is a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms. Preferably, at least one of them is a fluorine atom or a saturated hydrocarbon group having 1 to 4 carbon atoms.

In terms of heat resistance and light resistance, at least one of R ^13A to R ^14A is preferably a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and more preferably at least either one is a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms. Preferably, at least one of them is a fluorine atom or a saturated hydrocarbon group having 1 to 4 carbon atoms.

R ^15A to R ^20A are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a saturated hydrocarbon group having 1 to 4 carbon atoms, and hydrogen It is more preferably an atom or a methyl group.

R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ are each independently preferably 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 a halogen atom or an alkoxy group having 1 to 4 carbon atoms. , an aromatic hydrocarbon group optionally substituted with a hydroxyl group or a methylsulfonyl group or a saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group represented by the following formula Do. 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. The number of halogen atoms in the aromatic hydrocarbon group represented by R ⁵⁵ is preferably 1 to 6, more preferably 1 to 4, still more preferably 2 to 3. It is preferable that the said halogen atom is a fluorine atom.

It is especially preferable that R ⁵⁵ is an aromatic hydrocarbon group represented by a following formula. In the following formula, * represents a bond.

(Formula 7)

(Formula 8)

Examples of the r-valent metal ion represented by M ^r+ 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, cobalt ion, nickel ion, copper ion. transition metal ions such as; zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, and typical metal ions such as bismuth ions, and alkaline earth metal ions, transition metal ions or typical metal ions are preferable. , magnesium ion, strontium ion, barium ion, manganese ion, or zinc ion is more preferable, and barium ion is still more preferable.

It is preferable that r is 2-5, More preferably, it is 2-4, More preferably, it is 2-3.

In formula (A-I), the number of M ^r+ is the number obtained by dividing the number by r by one less than the number (k) of -SO ₃ ^- in the compound represented by formula (AI) ((k-1) )/r) becomes For this reason, compound (AI) becomes a valence of 0, ie, an electrically neutral compound.

In formula (AI), the number of objects (k) of -SO ₃ ^- is 2 or more, it is preferable that it is 6 or less, More preferably, it is 4 or less.

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

In the above (a) to (c), -SO ₃ ^- is preferably directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group or the aralkyl group. That is, it is preferable that -SO ₃ ^- has substituted the hydrogen atom couple|bonded with the aromatic hydrocarbon ring.

Two or more -SO ₃ ^- may be bonded to the same aromatic hydrocarbon ring, but is preferably bonded to different aromatic hydrocarbon rings.

As compound (A-I), as shown to following Tables 1 - Table 9, the compound 1 - compound 514 etc. which are represented by a formula (A-I-1) are mentioned. In the formula, * represents a bond.

However, the compound represented by formula (A-I-1) has two -SO ₃ ^- , two or more of R ^h and R ^11A to R ^14A are hydrogen atoms, and any two of them are - It is substituted with SO ₃ ⁻ , preferably R ^h is a hydrogen atom, and any two of them are substituted with —SO ₃ ⁻ , more preferably R ^h is a hydrogen atom, and a nitrogen atom In the benzene ring bonded to , R ^h positioned at the para position with respect to the bonding position with the nitrogen atom is substituted with —SO ₃ ^— .

(Formula 9)

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.

(Formula 10)

Especially, as a compound represented by Formula (AI),

Compound 31 to compound 90, compound 121 to compound 180, compound 211 to compound 334, compound 365 to compound 424, and compound 455 to 514 are preferred;

Compound 46 to compound 60, compound 61 to compound 90, compound 136 to compound 150, compound 226 to compound 240, compound 271 to compound 334, compound 380 to compound 394, and compound 470 to 484 are more preferable;

Compound 46 to compound 60, compound 61 to compound 90, compound 136 to compound 150, compound 226 to compound 240, compound 271 to compound 304, compound 380 to compound 394, and compound 470 to 484 are more preferable;

more preferably compound 46 to compound 60, compound 61 to compound 90, compound 136 to compound 150, compound 226 to compound 240, compound 271 to compound 294, compound 380 to compound 394, and compound 470 to 484,

Compound 46 to compound 60, compound 61 to compound 90, compound 136 to compound 150, compound 226 to compound 240, compound 279 to compound 294, compound 380 to compound 394, and compound 470 to 484 are particularly more preferable.

Compound (AI), for example, sulfonates the salt represented by the formula (A-y) to give the salt represented by the formula (A-x), and further, an acetate salt of an r-valent metal ion M ^r+ ; It can be prepared by reacting with carbonate, phosphate, sulfate, silicate, cyanide or halide (preferably chloride).

(Formula 11)

[in formula (A-y),

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 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent. , wherein the aromatic hydrocarbon group and the aralkyl group do not have —SO ₃ ^— as a substituent,

R ^11B to R ^20B each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom,

In R ^1B to R ^20B , the methylene group included 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, and the aromatic hydrocarbon group is —SO ₃ ^— as a substituent do not have,

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, wherein the aromatic hydrocarbon group does not have —SO ₃ ^— as a substituent;

In R ^45B , R ^46B , and R ^55B , the methylene group included in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-;

A _B ^j- represents an anion of any j valence,

j represents an integer of 1 or more and 5 or less.]

As A _B ^j- , a chlorine ion, a phosphate ion, a sulfate ion, a benzenesulfonate ion, a naphthalenesulfonic acid ion, a perchlorate ion, _BF4- ^, _PF6- ^, etc. are mentioned, for example.

(Formula 12)

[In formula (A-x), R ^1A to R ^20A , R ⁴⁵ , R ⁴⁶ , R ⁵⁵ , and k are the same as above, A _A ^z+ represents an arbitrary z-valent cation, and z is 1 or more 5 The following integers are shown.]

A _A ^z+ is preferably hydro.

As a method of sulfonation, various well-known methods, for example, the method described in Journal of Organic Chemistry, (1994), Vol.59, #11, p.3232-3236 are mentioned.

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

Specific examples of the blue pigment include compounds classified as pigments in the Color Index (published by The Society 　 of Dyers 　 and Colorists) and compounds described in Japanese Patent Application Laid-Open No. 2017-16100.

Specifically, for example, C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60; etc. are mentioned. Among them, C.I. It is preferable to contain pigment blue 15:6. In addition, as a purple pigment, for example, C.I. You may contain Pigment Violet 19 and 23.

Examples of the dye include compounds classified as acid dyes, direct dyes, basic dyes, disperse dyes, and useful dyes in the Color Index (published by The Society of Dyers and Colorists). For example,

Acid Arizarin 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 Chrome Violet　K;

Acid Fluffy;

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; Alternatively, derivatives of these dyes are mentioned.

It is preferable that it is 80-99.99 mass %, It is more preferable that it is 85 mass % or more, and, as for the content rate of the said blue coloring agent, it is more preferable that it is 90 mass % or more in 100 mass % of solid content of a coloring agent from a viewpoint of high saturation.

If necessary, the blue colorant may be subjected to rosin treatment, surface treatment using a pigment derivative introduced with acidic or basic groups, etc., graft treatment to the pigment surface with a polymer compound, etc., atomization treatment by sulfuric acid atomization method, etc., or to remove impurities A cleaning treatment with an organic solvent, water, or the like, or a treatment for removing ionic impurities by an ion exchange method or the like may be performed.

When a blue coloring agent contains a dispersing agent and performs a dispersion process, it turns into a blue coloring agent dispersion liquid of the state disperse|distributed uniformly in a solution.

Surfactants are mentioned as said dispersing agent, Any surfactant among cationic, anionic, nonionic, and amphoteric types may be sufficient. Specific examples thereof include dispersants such as polyester, polyamine, and acrylic. These dispersants may be used individually or in combination of 2 or more type. As a dispersing agent, KP (Shin-Etsu Chemical Co., Ltd. product), Florene (Kyoeisha Chemical Co., Ltd. product), Solsperse (trademark) (Zeneca Co., Ltd. product), EFKA (registered trademark) (BASF) are trade names as a dispersing agent. company), Addisper (trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemi), and the like. You may use resin (B) mentioned later as a dispersing agent.

When using a dispersing agent, the usage-amount becomes like this with respect to 100 mass parts of blue coloring agents. Preferably it is 100 mass parts or less, More preferably, they are 5 mass parts or more and 75 mass parts or less. When the usage-amount of a dispersing agent exists in the said range, there exists a tendency for the dispersion liquid in a uniformly dispersed state to be obtained.

It is preferable that content rate of a blue coloring agent is 1-50 mass % in 100 mass % of blue coloring agent dispersion liquids, It is more preferable that it is 2-30 mass %, It is still more preferable that it is 3-20 mass %. When using 2 or more types, you may mix a blue coloring agent at the time of use as a dispersion liquid, respectively.

It is preferable that it is 0.1-40 mass % in 100 mass % of blue coloring curable resin composition, as for content rate of a blue coloring agent, it is more preferable that it is 0.5-30 mass %, It is more preferable that it is 1-20 mass %.

<Compound Y>

Compound Y is a compound satisfying the following conditions 1) to 3) when the spectral spectrum of a cyclohexanone solution containing 0.001 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 3 or more at maximum absorption wavelength

Condition 3) Absorbance 0.2 or less at 460 nm

For the maximum absorption wavelength and absorbance of compound Y, prepare a cyclohexanone solution containing 0.001 mass % of compound Y, and then pour the solution into a measuring vessel (eg, cuvette) with an optical path length of 1.0 cm. It can be measured by using an ultraviolet-visible near-infrared spectrophotometer. Absorbance is shown as a relative value with respect to 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, still more preferably 395 nm or more, further preferably 445 nm or less, more preferably 440 nm or less. The compound Y which satisfies the related conditions can improve brightness with a blue coloring agent.

The absorbance in the maximum absorption wavelength of compound Y is 3 or more, Preferably it is 3.2 or more, More preferably, it is 3.4 or more, More preferably, it is 3.6 or more, More preferably, it is 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, still more preferably 0.12 or less.

The thermal decomposition temperature of the 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.

The compound Y is preferably a porphyrin compound, a melocyanine compound, or a methine compound, and more preferably a porphyrin compound.

In the porphyrin compound, an aromatic ring group or a heterocyclic group which may have a substituent may be bonded to the porphine ring. Although a phenyl group, a naphthyl group, a tolyl group, and a xylyl group are mentioned as aromatic ring, Preferably it is a phenyl group. Examples of the heterocyclic group include a pyridine group, a pyradine group, and a pilimidine group. A C1-C4 alkoxy group, a hydroxyl group, a carboxyl group etc. may be sufficient as a substituent. When the aromatic ring group or heterocyclic group which may have a substituent is couple|bonded, 1-8 are preferable, as for the number of groups to couple|bond, 2-4 are more preferable, and it is still more preferable that it is 4. When two or more aromatic ring groups or heterocyclic groups which may have a substituent couple|bond, they may be same or different, and the same thing is preferable.

The porphyrin compound may or may not form a complex. When a porphyrin compound forms a complex, it is preferable that Cu, Pd, Co, Ni, Fe, or Zn coordinate to form a complex, and it is more preferable that Cu coordinates to form a complex. In addition, the porphyrin compound does not contain a tetraazaporphyrin compound.

As the porphyrin compound, for example, a visible light absorbing material (Yamada Chemical Industries, Ltd. FDB-002), 5,10,15,20-tetraphenyl-21H, 23H-porphine copper(II), tetraphenylporphyrin, etc. are available. Do.

The compound Y may contain 1 type(s) or 2 or more types.

The total content of the compound Y is preferably 0.01 to 20% by mass, more preferably 15% by mass or less, still more preferably 10% by mass or less in 100% by mass of the colorant.

It is preferable that it is 0.001-20 mass % in 100 mass % of blue coloring curable resin composition, as for the total content rate of the compound Y, It is more preferable that it is 0.005-15 mass %, It is still more preferable that it is 0.01-10 mass %.

<Resin (B)>

Although resin (B) is not specifically limited, It is preferable that it is an alkali-soluble resin, At least 1 type (a) (hereinafter referred to as "(a)") selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride A resin having a structural unit derived from ) is more preferable. The resin (B) further has a structural unit derived from a monomer (b) (hereinafter sometimes referred to as “(b)”) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, (a) Structural unit derived from monomer (c) copolymerizable with and (however, (a) and (b) are different.) (hereinafter sometimes referred to as "(c)"), and an ethylenically unsaturated bond in the side chain It is preferable to have at least one kind of structural unit selected from the group consisting of structural units having.

Specifically as (a), for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono[2-(meth)acryloyl oxyethyl], etc. are mentioned, Preferably, they are acrylic acid, methacrylic acid, and maleic anhydride.

(b) is a monomer having a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and a (meth)acryloyloxy group is preferable

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

As (b), for example, glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate 3-ethyl- 3-(meth)acryloyloxymethyloxetane tetrahydrofurfuryl (meth)acrylate etc. are mentioned, Preferably, glycidyl (meth)acrylate, 3,4-epoxy tricyclo [5.2. 1.0 ^2,6 ] It is decyl (meth)acrylate and 3-ethyl-3- (meth)acryloyloxymethyloxetane.

As (c), for example, methyl (meth) acrylate, butyl (meth) acrylate cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]Decan-8-yl (meth)acrylate benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyl Toluene etc. are mentioned, Preferably, styrene, vinyltoluene, N-phenyl maleimide, N-cycle hexyl maleimide, N-benzyl maleimide, etc. 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 adding (a) to the copolymer of (b) and (c). It can be manufactured by The resin may be a resin in which (a) is added to the copolymer of (b) and (c) and further reacted with carboxylic acid anhydride.

The weight average molecular weight of resin (B) in terms of polystyrene becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of resin (B) becomes like this in conversion of solid content, Preferably it is 50-170 mg-KOH/g, More preferably, it is 60-150 mg-KOH/g, More preferably, it is 70-135 mg-KOH/g. Here, an acid value is a value measured as quantity (mg) of potassium hydroxide required in order to neutralize 1 g of resin (B), For example, it can obtain|require by titrating using potassium hydroxide aqueous solution.

To [ the content rate of resin (B) ] with respect to the total amount of solid content, Preferably it is 7-65 mass %, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %.

<Colorant (A2)>

The blue coloring curable resin composition of this invention may contain dye (A2-1) and pigment (A2-2) other than a coloring agent (A1) as a coloring agent (A2).

The dye (A2-1) is not specifically limited, A well-known dye can be used, For example, a solvent dye, an acid dye, a direct dye, a mordant dye, etc. are mentioned. As the dye, for example, a compound classified as having a color other than a pigment in the Color Index (published by The Society of Dyers and Colorists), and a known dye described in a dyeing note (dyed yarn) can be mentioned. . In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, scrylium dyes, azo dyes Creidine dye, styryl dye, coumarin dye, quinoline dye, nitro dye, etc. are mentioned. Among these, organic solvent-soluble dyes are preferable. In addition, as a dye, you may use the thing of Unexamined-Japanese-Patent No. 2015-28121, Unexamined-Japanese-Patent No. 2013-7032, Unexamined-Japanese-Patent No. 2013-144724, Unexamined-Japanese-Patent No. 2013-53292, etc. It does not specifically limit as a pigment (A2-2), A well-known pigment can be used, For example, the pigment classified as a pigment by the color index (The Society of the Dyers and Colorists publication) is mentioned.

As the pigment, for example, C.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 , 147, 148, 150, 153, 154, 166, 173, 194, 214 yellow pigments;

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

C.I. Red pigments such as 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 the like.

To [ the content rate of a coloring agent (A2) ] with respect to the total amount of solid content, Preferably it is 0.1-60 mass %, More preferably, it is 0.5-55 mass %, More preferably, it is 1-50 mass %.

Here, the "total amount of solid content" in this specification means the quantity which removed content of the solvent from the total amount of blue coloring curable resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, etc., preferably Preferably, it is a (meth)acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has three or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , dipentaerythritol hexa(meth)acrylate, and the like.

The weight average molecular weight of a polymeric compound (C) becomes like this. Preferably it is 150 or more and 2,900 or less, More preferably, they are 250 or more and 1,500 or less.

It is preferable that content rate of a polymeric compound (C) is 7-65 mass % with respect to the total amount of solid content, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating an active radical, an acid, etc. under the action of light or heat, and a known polymerization initiator can be used. As a polymerization initiator which generate|occur|produces an active radical, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulf), for example. Panylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine 2-methyl-2-morphol no-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexylphenyl Ketone 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(2-chloro phenyl)-4,4', 5,5'-tetraphenylbiimidazole, etc. are mentioned.

To [ content of a polymerization initiator (D) / 100 mass parts of total amounts of resin (B) and a polymeric compound (C)), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. When content of a polymerization initiator (D) exists in said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, productivity of a color filter improves.

The blue colored curable resin composition of this invention may contain the polymerization initiation adjuvant.

<Polymerization initiation aid (D1)>

The polymerization initiation adjuvant (D1) is a compound or sensitizer used in order to accelerate|stimulate superposition|polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator. When a polymerization initiation adjuvant (D1) is included, it is used in combination with a polymerization initiator (D) normally.

Examples of the polymerization initiation auxiliary (D1) include 4,4'-bis(dimethylamino)benzophenone (common name mihirazketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone N-phenylglycine etc. are mentioned.

When using these polymerization initiation adjuvant (D1), the content is with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. is the mass part. When the amount of the polymerization initiation auxiliary (D1) is within this range, a coloring pattern can be formed with a higher sensitivity, and the productivity of the color filter tends to be improved.

It is preferable that the blue coloring curable resin composition of this invention contains a solvent.

<Solvent (E)>

The solvent (E) is not specifically limited, The solvent normally used in this field|area can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether esters Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (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 solvent include ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone ( Solvent containing -COO- and not containing -O- in the molecule); Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol Ether solvents, such as dimethyl ether and diethylene glycol methyl ethyl ether (solvent containing -O- in a molecule|numerator and not containing -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, and diethylene glycol monoethyl ether acetate (in the molecule Solvent containing -COO- and -O-);

Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, and cyclohexanone (with -CO- in the molecule and not -COO- Solvent); Alcohol solvents, such as butanol, cyclohexanol, and propylene glycol (The solvent which contains OH in a molecule|numerator and does not contain -O-, -CO-, and -COO-); etc. are mentioned. and 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 included, the content rate of the solvent (E) is preferably 70 to 95 mass %, more preferably 75 to 92 mass % with respect to the total amount of the blue colored curable resin composition of the present invention. . In other words, the total amount of solid content of blue coloring curable resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When content of a solvent (E) exists in said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

<Other ingredients>

If necessary, the blue colored curable resin composition of the present invention may contain additives known in the art, such as leveling agents, fillers, other high molecular compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents.

<The manufacturing method of blue colored curable resin composition>

The blue colored curable resin composition of the present invention can be prepared by mixing a colorant (A1), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E) and other components as needed. there is.

<The manufacturing method of a color filter>

As a method of manufacturing a coloring pattern with the blue coloring curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable.

In the color filter of the present invention, it is preferable that the coordinates (x, y) in the xy chromaticity diagram in the CIE1931 color space measured using the characteristic function of the C light source satisfy the relationship of x ² +y ² ≤ 0.035, , x ² +y ² ≤ 0.030 is more preferably satisfied, and the coordinates (x, y) in the xy chromaticity diagram in the CIE1931 color space are (0.120, 0.080), (0.120, 0.105), (0.136) , 0.080) and (0.136, 0.105) are more preferable.

When blue coloring curable resin composition contains a blue coloring agent and the compound Y as a coloring agent, the color filter excellent in the brightness especially in a high chroma area|region can be produced. The color filter is useful as a color filter used for a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not inherently limited by the following examples, and is carried out with appropriate changes within the range that can be suitable for the gist of the preceding and latter period. It is of course possible, and they are all included in the technical scope of the present invention.

[Synthesis Example 1]

The following reaction was performed in nitrogen atmosphere. 50 parts of the compound represented by Formula (C-I-2) and 188 parts of N,N- dimethylformamide were thrown into the flask provided with the cooling tube and the stirring apparatus, and it stirred for 30 minutes, cooling in an ice bath. 40 parts of potassium tert-butoxide (made by Tokyo Chemical Industry Co., Ltd.) was thrown into the said flask, and it stirred for 1 hour further, cooling in an ice bath. 55.6 parts of iodine ethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while the reaction solution was cooled on ice. The reaction solution was heated to 35°C using an oil bath and stirred for 5 hours, and then left to cool to room temperature. In another flask equipped with a stirring device, 1000 parts of a 10% aqueous sodium chloride solution was put, and the reaction solution was added dropwise while stirring. After stirring for 30 minutes, a solid was obtained by filtration. 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 a compound represented by the formula (C-I-3). Yield 93.5%.

(Formula 13)

(Formula 14)

The following reaction was performed in nitrogen atmosphere. After putting 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile to the flask provided with a cooling tube and a stirring apparatus, it stirred under room temperature for 30 minutes. After 40.0 parts of 2,6-difluorobenzoic acid chloride (made by Tokyo Chemical Industry Co., Ltd.) was dripped at the said flask over 30 minutes, it stirred at room temperature for 1 hour. After 30.6 parts of N-ethyl-o-toluidine (made by Tokyo Chemical Industry Co., Ltd.) was dripped at the said flask over 30 minutes, it stirred at room temperature for 1 hour. An aqueous solution in which 79.2 parts of sodium monochloroacetate was dissolved in 120 parts of ion-exchanged water was put into the flask, and 60.4 parts of a 30% aqueous sodium hydroxide solution was added, followed by stirring at room temperature for 18 hours. After further adding 600 parts of ion-exchange water to the said flask, it stirred for 1 hour, and the yellowish-white solid which precipitated was filtered. The obtained off-white solid was washed with 120 parts of acetonitrile and then washed with 560 parts of ion-exchanged water. The washed off-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 stirring device, followed by stirring at room temperature for 2 hours. After 80.8 parts of 30% sodium hydroxide aqueous solution was dripped here over 10 minutes, it stirred for 5 minutes, and liquid separation operation removed the water layer. 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 and liquid-separation washing|cleaning was carried out. After concentrating the obtained organic layer with an evaporator, it dried under reduced pressure at 35 degreeC, and obtained the compound represented by Formula (B-I-3) as a white solid. The quantity was 43.4 parts, and the yield was 58.0%.

(Formula 15)

The following reaction was performed in nitrogen atmosphere. After putting 13.2 parts of compounds represented by Formula (B-I-3), 19.0 parts of compounds represented by Formula (C-I-3), and 38 parts of toluene to the flask provided with a cooling tube and a stirring apparatus, then, oxychloride Phosphorus 9.2 parts was added, and it stirred at 100 degreeC for 7 hours. The reaction mixture was then cooled to room temperature, and then diluted with 29 parts of methyl ethyl ketone. Next, the mixed solution of 114 parts of ion-exchange water and 10 parts of 35% hydrochloric acid aqueous solution was poured into the diluted reaction mixture, and liquid separation operation removed the water layer. After solvent-distilling the obtained organic layer with the evaporator, the compound represented by Formula (X-II-7) was obtained as a bluish purple solid by drying at 60 degreeC under reduced pressure. The amount of blue-violet solid was 39.4 parts.

(Formula 16)

The following reaction was performed in nitrogen atmosphere. 38.4 parts of compounds represented by Formula (X-II-7) and 112 parts of methyl chlorides were thrown into the flask provided with the cooling tube and a stirring apparatus, and it stirred for 30 minutes. After cooling the reaction solution on ice and maintaining the internal temperature 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. Subsequently, the reaction solution was cooled on ice and while maintaining the internal temperature at 10°C, it was diluted with a mixed solution of 64 parts of N,N-dimethylformamide and 4.9 parts of ion-exchanged water. After pouring the diluted reaction solution into 1120 parts of toluene, when it stirred for 30 minutes, a viscous solid precipitated. After discharging the oil layer by decantation, 320 parts of toluene was added to the obtained viscous solid, followed by stirring for 30 minutes. To the viscous solid obtained by discharging the oil layer by decantation, 832 parts of 20% saline was added and stirred for 1 hour, and then the blue solid was filtered out by filtration. The obtained blue solid was wash|cleaned with 576 parts of 20% saline, and it dried under reduced pressure at 35 degreeC. The obtained solid and 128 parts of methanol were put into a flask equipped with a stirring device, and the mixture was stirred for 30 minutes, followed by filtration and separation into a solid and a filtrate. Let this filtrate be filtrate A3. The solid collected by filtration was washed with 192 parts of methanol, and filtration was performed to separate the solid and the filtrate. Let this filtrate be filtrate B3. After mixing the filtrate A3 and the filtrate B3 and removing the solvent with an evaporator, it dried under reduced pressure at 40 degreeC and obtained the compound represented by Formula (X-I-7) as a bluish purple solid. The quantity (收量) of the blue-violet solid was 38.3 parts.

(Formula 17)

28.0 parts of the compound represented by Formula (X-I-7), 43.2 parts of barium chloride dihydrate, and 356 parts of ion-exchange water were added to the flask provided with a cooling tube and a stirring apparatus, After stirring at 40 degreeC for 2 hours, reaction suspension was filtered. The solid obtained by filtration and 350 parts of ion-exchanged water were thrown into the flask provided with the stirring device, and after stirring for 30 minutes, the suspension was filtered. After wash|cleaning the obtained solid with 280 parts of ion-exchange water, it dried under reduced pressure at 60 degreeC, and obtained the compound represented by Formula (A-I-7) as a blue-violet solid. The yield was 24.5 parts and the yield was 81.7%.

(Formula 18)

Identification of the compound represented by formula (A-I-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)

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed into the flask, replaced with a nitrogen atmosphere, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were placed, and the mixture was heated to 85° C. while stirring. Next, 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 ]deca-9-ylacrylic A mixed solution of 25 parts of the mixture (content is 1:1), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was dripped over 5 hours. On the other hand, the mixed solution which melt|dissolved 5 parts of 2, 2- azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was dripped over 6 hours. After completion|finish of dripping, after maintaining at the same temperature for 4 hours, it cooled to room temperature, and obtained the copolymer (resin (B-1)) solution with a B type viscosity (23 degreeC) 23 mPas, and solid content 25.6%. The resulting copolymer had a weight average molecular weight Mw of 8000, a solid dispersion value of 111 mg-KOH/g, and a dispersion degree of 2.1. Resin (B-1) has the following structural unit.

(Formula 19)

[Preparation of Dispersion 1]

After weighing out 8.2 parts of compound (A-I-7), 6.1 parts of dispersant BYKLPN-6919 (in terms of solid content), 2.1 parts of resin (B-1) (in terms of solid content) as a resin, and 84 parts of propylene glycol monomethyl ether acetate , 600 parts of 0.4 µm zirconia beads were put, and after shaking for 1 hour using a paint conditioner (manufactured by LAU), the zirconia beads were removed by filtration to prepare a dispersion liquid 1.

[Preparation of Dispersion 2]

C.I. Pigment Blue 15:6 (pigment) 10 parts, acrylic pigment dispersant (solid content conversion) 3.5 parts, Resin (B-1) (solid content conversion) 4 parts, propylene glycol monomethyl ether acetate 80 parts , 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 3]

C.I. 13 parts of Pigment Yellow 150 (pigment), 3.9 parts of an acrylic pigment dispersant (in terms of solid content), 6.1 parts of Resin (B-1) (in terms of solid content) as a resin, and 77 parts of propylene glycol monomethyl ether acetate are mixed, The pigment was sufficiently dispersed using a bead mill to prepare a dispersion liquid 3.

<Preparation of blue colored curable resin composition>

[Example 1]

The blue coloring curable resin composition was obtained by mixing the following component.

Blue colorant: Dispersion 1 454 parts

Blue colorant: dispersion 2　 192 parts

Compound Y: Y-1: Porphyrin compound (FDB-002 (thermal decomposition temperature of 340° C.); manufactured by Yamada Chemical Industry Co., Ltd.) 0.33 parts

Resin (B): Resin (B-1) (in terms of solid content) 33 parts

Polymeric compound (C): 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF; O-acyloxime compound) 8.0

Solvent (E): 146 parts of cyclohexanone

Solvent (E): 759 parts of propylene glycol monomethyl ether acetate

Solvent (E): 19 parts of ethyl lactate

Leveling agent (H): 0.16 parts of polyether-modified silicone oil (in terms of solid content) (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Preparation of blue colored curable resin composition>

[Example 2]

Instead of using 0.33 parts of Y-1, carry out except using 0.8 parts of 5,10,15,20-tetraphenyl-21H, 23H-porphine copper (II) (Aldrich Corporation: hereinafter referred to as Y-2). It carried out similarly to Example 1, and obtained blue coloring curable resin composition.

<Measurement of the spectral spectrum of compound Y>

Compound Y was dissolved in cyclohexanone to obtain a solution so that the concentration was 0.001% by mass. The spectral spectrum of the cyclohexanone single solution as the solution and blank was measured using an ultraviolet visible near-infrared spectrophotometer (V-650; manufactured by Nippon Spectroscopy Co., Ltd.; quartz cell with a 1.0 cm corner). A result is shown in Table 10.

<Production of the coloring pattern>

After apply|coating blue colored curable resin composition by the spin coating method on the glass substrate (Eagle 2000; Corning company make) of 5 cm corner, it prebaked at 100 degreeC for 3 minutes, and the coloring composition layer was formed. After cooling, the interval between the substrate on which the coloring 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 in an atmospheric atmosphere, and an exposure dose of 60 mJ/cm 2 (based on 365 nm) was irradiated with light. As a photomask, the thing in which the 100 micrometers line-and-space pattern was formed was used. The coloring composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24° C. for 60 seconds, and after washing with water, post-baking at 230° C. for 20 minutes in an oven It carried out and obtained the coloring pattern.

<Measurement of film thickness>

About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). A result is shown in Table 11.

<Chromaticity evaluation>

About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd. product), and xy chromaticity coordinates (x, y) in the CIE1931 color space system using the characteristic function of the C light source and The stimulus value Y was measured. It shows that the brightness is so high that the value of Y is large. A result is shown in Table 11.

<Preparation of blue colored curable resin composition>

[Example 3]

The blue coloring curable resin composition was obtained by mixing the following component.

Blue colorant: Dispersion 1 258 parts

Blue colorant: 126 parts of dispersion 2

Compound Y: Y-1: Porphyrin compound (FDB-002; manufactured by Yamada Chemical Industry Co., Ltd.)

0.24 copies

Resin (B): 40 parts of resin (B-1) (in terms of solid content)

Polymeric compound (C): 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF; O-acyloxime compound) 8.0

Solvent (E): 119 parts of cyclohexanone

Solvent (E): 728 parts of propylene glycol monomethyl ether acetate

Solvent (E): 23 parts of ethyl lactate

Leveling agent (H): 0.13 parts of polyether-modified silicone oil (solid content conversion) (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

<Preparation of blue colored curable resin composition>

[Example 4]

The blue coloring curable resin composition was obtained by mixing the following component.

Blue colorant: Dispersion 1 241 parts

Blue colorant: Dispersion 2 140 parts

Compound Y: Y-2: 5,10,15,20-tetraphenyl-21H, 23H-porphine copper (II) (manufactured by Aldrich) 0.76 parts

Resin (B): 39 parts of resin (B-1) (in terms of solid content)

Polymeric compound (C): 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF; O-acyloxime compound) 8.0

Solvent (E): 119 parts of cyclohexanone

Solvent (E): 731 parts of propylene glycol monomethyl ether acetate

Solvent (E): 23 parts of ethyl lactate

Leveling agent (H): 0.13 parts of polyether-modified silicone oil (in terms of solid content) (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

<Preparation of blue colored curable resin composition>

[Comparative Example 1]

The blue coloring curable resin composition was obtained by mixing the following component.

Blue colorant: Dispersion 1 175 parts

Blue colorant: 379 parts of dispersion 2

Dispersion 3 11.6 parts

Resin (B): 31 parts of resin (B-1) (in terms of solid content)

Polymeric compound (C): 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF; O-acyloxime compound) 8.0

Solvent (E): 119 parts of cyclohexanone

Solvent (E): 761 parts of propylene glycol monomethyl ether acetate

Solvent (E): 18 parts of ethyl lactate

Leveling agent (H): Polyether-modified silicone oil (solid content conversion) (Toray Silicone)

SH8400; Tore Dow Corning Co., Ltd.) 0.15 parts

<Production of the coloring pattern>

After apply|coating blue colored curable resin composition by the spin coating method on the glass substrate (Eagle 2000; Corning company make) of 5 cm corner, it prebaked at 100 degreeC for 3 minute(s), and the coloring composition layer was formed. After leaving to cool, the interval between the substrate on which the coloring 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 in an atmospheric atmosphere at an exposure dose of 60 mJ/cm 2 (365 nm). standard) and irradiated with light. As a photomask, the thing in which the 100 micrometers line-and-space pattern was formed was used. The coloring composition layer after light irradiation is immersed and developed in an aqueous developer solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, and after washing with water, post-baking at 230°C for 20 minutes in an oven and a coloring pattern was obtained.

<Measurement of film thickness>

About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). A result is shown in Table 12.

<Chromaticity evaluation>

About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd. product), and xy chromaticity coordinates (x, y) in the CIE1931 color space system using the characteristic function of the C light source and The stimulus value Y was measured. It shows that the brightness is so high that the value of Y is large. A result is shown in Table 12.

<Preparation of blue colored curable resin composition>

[Example 5]

The blue coloring curable resin composition was obtained by mixing the following component.

Blue colorant: Dispersion 1 285 parts

Blue colorant: 190 parts of dispersion 2

Compound Y: Y-3: tetraphenyl porphyrin (Cas No. 917-23-7, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.73 parts

Resin (B): 48 parts of resin (B-1) (in terms of solid content)

Polymeric compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 61 parts

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF; O-acyloxime compound) 10 copies

Solvent (E): 146 parts of cyclohexanone

Solvent (E): 876 parts of propylene glycol monomethyl ether acetate

Solvent (E): 28 parts of ethyl lactate

Leveling agent (H): 0.16 parts of polyether-modified silicone oil (in terms of solid content) (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

<Measurement of the 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 solution and the cyclohexanone alone solution as the blank was measured using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by Nippon Spectroscopy Co., Ltd.; quartz cell with a corner of 1.0 cm). A result is shown in Table 13.

<Production of the coloring pattern>

After apply|coating blue colored curable resin composition by the spin coating method on the glass substrate (Eagle 2000; Corning company make) of 5 cm corner, it prebaked at 100 degreeC for 3 minute(s), and the coloring composition layer was formed. After cooling, the interval between the substrate on which the coloring 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 in an atmospheric atmosphere, and an exposure dose of 60 mJ/cm 2 (based on 365 nm) ) was irradiated with light. As a photomask, the thing in which the 100 micrometers line-and-space pattern was formed was used. The coloring composition layer after light irradiation was immersed and developed in an aqueous developer solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, and after washing with water, post-baking at 230°C for 20 minutes in an oven and a coloring pattern was obtained.

<Measurement of film thickness>

About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). A result is shown in Table 14.

<Chromaticity evaluation>

About the obtained coloring pattern, the spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd. product), and xy chromaticity coordinates (x, y) in the CIE1931 color space system using the characteristic function of the C light source and The stimulus value Y was measured. It shows that the brightness is so high that the value of Y is large. A result is shown in Table 14.

Claims (6)

a colorant, a resin, a polymerizable compound, and a polymerization initiator;
The colorant is a colorant comprising compound Y and a blue colorant,
The compound Y satisfies the following conditions 1) to 3) when the spectral spectrum of a cyclohexanone solution containing 0.001 mass % of the compound Y is measured with an optical path length of 1.0 cm, and is a porphyrin compound A blue colored curable resin composition to be
Condition 1) Maximum absorption wavelength 380 nm or more and 450 nm or less
Condition 2) Absorbance 3 or more at maximum absorption wavelength
Condition 3) Absorbance 0.2 or less at 460 nm According to claim 1,
Blue coloring curable resin composition whose content rate of a blue coloring agent is 80 mass % - 99.99 mass % in 100 mass % of coloring agents. 3. The method of claim 1 or 2,
Blue colored curable resin composition whose total content rate of compound Y is 0.01 mass % - 20 mass % in 100 mass % of coloring agents. The color filter formed from the blue coloring curable resin composition of Claim 1 or 2. 5. The method of claim 4,
A color filter in which the coordinates (x, y) in the xy chromaticity diagram in the CIE1931 color space measured using the characteristic function of the C light source satisfy the relation of x ² +y ² ≤ 0.035. A display device comprising the color filter according to claim 5 .