JP6268822B2 - Color material, color material dispersion, and resin composition - Google Patents

Description

  The present invention relates to a color material, a color material dispersion containing the color material, and a resin composition containing the color material.

Near-infrared absorbing pigments include, for example, infrared absorbing filters, heat ray absorbing filters, bandpass filters, invisible printing inks, infrared absorbing paints, flash toners, electrophotographic photoreceptors, sensitizers, optical recording materials such as optical disks, optical sensors, etc. It is also used for applications such as plate making using an infrared laser. As such near-infrared absorbing dyes, polymethine dyes, phthalocyanine dyes, aminium dyes, diimonium dyes, and the like are known. From the viewpoint of excellent near-infrared absorption, aminium dyes and diimonium dyes are used. Widely used.
Aminium dyes and diimonium dyes generally have a merit that they are hard to be colored because they absorb less visible light than phthalocyanine dyes, while aminium dyes and diimonium dyes generally have low heat resistance and light resistance. There was a problem.

  Various methods have been tried to improve various resistances of aminium dyes and diimonium dyes.

  Patent Document 1 discloses a diimonium salt compound comprising a specific diimonium cation and a specific monovalent anion. According to Patent Document 1, the specific diimonium salt compound is said to be excellent in heat resistance and moist heat resistance. However, the diimonium salt compound of Patent Document 1 is insufficient in both heat resistance and light resistance.

  Patent Document 2 discloses a specific diimonium salt compound in which a specific diimonium cation and two types of monovalent anions are combined. According to Patent Document 2, it is said that the specific diimonium salt compound is excellent in heat resistance and moist heat resistance. However, the diimonium salt compound of Patent Document 2 is insufficient in both heat resistance and light resistance.

Japanese Patent No. 49342320 International Publication No. 2008/010501 Pamphlet

  The present invention has been made in view of the above circumstances, a colorant excellent in heat resistance and light resistance, a colorant dispersion capable of forming a coating film excellent in heat resistance and light resistance, and a resin composition The purpose is to provide.

  The coloring material according to the present invention is a compound represented by the following general formula (I).

(In general formula (I), A represents a cation containing at least one selected from the following general formula (II) and the following general formula (III), and X ^a- represents an a-valent heteropolyacid anion. a represents a number of 2 or more, and b and c represent a number of 1 or more.)

(In General Formula (II) and General Formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a substituent. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ are each independently bonded to each other to represent an alicyclic complex. A ring may be formed.)

  The colorant dispersion according to the present invention comprises a colorant represented by the general formula (I), a dispersant, and a solvent having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less. It is characterized by containing.

  The resin composition according to the present invention is characterized by containing the colorant represented by the general formula (I) and a binder component.

In the color material, the color material dispersion, and the resin composition according to the present invention, the X ^a- is an a-valent heteropolyacid anion containing at least one selected from a molybdenum atom and a tungsten atom. From the viewpoint of excellent heat resistance and light resistance.

  ADVANTAGE OF THE INVENTION According to this invention, the color material excellent in heat resistance and light resistance, the color material dispersion liquid which can form the coating film excellent in heat resistance and light resistance, and a resin composition can be provided.

Hereinafter, the coloring material, the coloring material dispersion, and the resin composition of the present invention will be described in detail in order.
In the present invention, the “coloring material” refers to a compound that absorbs at least a part of visible light (light having a wavelength of 400 nm to 700 nm) and near infrared light (light having a wavelength of 700 nm to 1100 nm). Absorbing compounds are also included.
In the present invention, (meth) acryl represents each of acryl or methacryl, and (meth) acrylate represents each of acrylate or methacrylate.

[Color material]
The coloring material according to the present invention is a compound represented by the following general formula (I).

(In general formula (I), A represents a cation containing at least one selected from the following general formula (II) and the following general formula (III), and X ^a- represents an a-valent heteropolyacid anion. a represents a number of 2 or more, and b and c represent a number of 1 or more.)

(In General Formula (II) and General Formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a substituent. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ are each independently bonded to each other to represent an alicyclic complex. A ring may be formed.)

The color material according to the present invention is excellent in heat resistance and light resistance. The reason is unclear, but is estimated as follows.
The coloring material of the present invention uses a divalent or higher heteropoly acid anion as a counter ion of an aminium cation and a diimonium cation. The heteropolyacid itself is excellent in heat resistance and light resistance. Further, by using a polyvalent heteropoly acid anion, the cation and the anion are not ion-bonded one-on-one, but two or more dye cations are ion-bonded to one heteropoly acid anion. Therefore, a plurality of cations centering on the heteropolyacid anion constitute one molecule. As a result, it is presumed that the apparent molecular weight is increased as compared with the conventional aminium dye or diimonium dye in which one aminium cation or diimonium cation constitutes one molecule, and the heat resistance is lowered to improve the heat resistance. .
In addition, since the heteropolyacid has high acidity and excellent anion stability, the stability of a pair of aminium cation and diimonium cation is improved. Therefore, it is presumed that the cation coloring property is stabilized and the light resistance is improved.
For these reasons, the coloring material of the present invention is excellent in heat resistance and light resistance, and is excellent in infrared absorption.

The hydrocarbon group in R ^{1 to} R ⁸ is not only an aliphatic hydrocarbon group, but also an aromatic hydrocarbon group in which the aliphatic hydrocarbon group may be substituted, or an aliphatic hydrocarbon in which the aromatic hydrocarbon is substituted. A hydrogen group is also included. The aliphatic hydrocarbon group may be linear, branched or cyclic. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
Examples of the hydrocarbon group for R ^{1 to} R ⁸ include an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon group substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms, An aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably used.

Specific examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group, which may be linear or branched. In addition, when the number of carbon atoms is 3 or more, it may be cyclic. Specific examples of the cyclic alkyl group include a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclopentylbutyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.
Specific examples of the aliphatic hydrocarbon group substituted by an aromatic hydrocarbon group having 6 to 10 carbon atoms include a benzyl group, a phenethyl group, and a phenylpropyl group.
Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms include condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring and phenanthrene ring in addition to benzene ring; Examples thereof include chain polycyclic hydrocarbons such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene.

Examples of the substituent that the hydrocarbon group may have include a hydroxyl group, a sulfonic acid group, a nitro group, an amino group, a cyano group, an alkoxy group, and a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferable.

R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ may be independently bonded to each other to form an alicyclic heterocycle containing a nitrogen atom. Examples of the aliphatic heterocyclic ring include piperidine, morpholine, indoline and the like, and the substituent may have a hydroxyl group, a sulfonic acid group, a nitro group, an amino group, a cyano group, an alkoxy group, or a halogen atom. .

As R ^{1 to} R ⁸ , from the viewpoint of heat resistance and light resistance, an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aliphatic hydrocarbon group having 6 to 10 carbon atoms are substituted. A group hydrocarbon group is preferred.
Specific examples of preferable substituents as R ^{1 to} R ⁸ include methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclohexylmethyl group, cyanopropyl group, trifluoromethyl group, trifluoroethyl group, hexafluoro group. An ethyl group, a trichloromethyl group, etc. are mentioned.

  In the color material of the present invention, the cation (A) is used alone or in combination of two or more of the cation represented by the general formula (II) and the cation represented by the general formula (III). be able to. In the present invention, from the viewpoint of heat resistance and light resistance, it is preferable to include a cation represented by the general formula (III).

In the color material of the present invention, a divalent or higher valent heteropolyacid anion is used as a counter anion (X ^a− ) of an aminium cation and a diimonium cation. By using such a heteropolyacid anion as a counter anion, the apparent molecular weight is increased as compared with an aminium dye or a diimonium dye, the heat resistance is improved, and the light resistance is also improved by suppressing fading due to oxidation.

The heteropolyacid anion used in the present invention is a divalent or higher valent heteropolyacid anion ion represented by the formula (L ₁ M _m O _n ) ^a- (a represents a number of 2 or more). In the ionic formula, L represents a hetero atom, M represents a poly atom, O represents an oxygen atom, and l, m, and n represent the composition ratio of each atom. Examples of the poly atom M include Mo, W, V, Ti, Nb, Al, Ta, and the like. The hetero atom L is not particularly limited, and examples thereof include Si, P, As, S, Fe, and Co. Moreover, a counter cation such as Na ⁺ or H ⁺ may be partially included.
In the present invention, the anion (X ^a− ) is preferably an a-valent heteropolyacid anion containing at least one selected from a molybdenum atom and a tungsten atom from the viewpoint of heat resistance and light resistance.

Specific examples of a divalent or higher valent heteropolyacid anion containing one or more of a molybdenum atom and a tungsten atom include, for example, Keggin-type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson-type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , β- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , Keggin-type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ⁴⁻ , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ⁴⁻ , and as other examples, [P ₂ W ₁₇ O ₆₁ ] ¹⁰⁻ , [P ₂ W ₁₅ O ₅₆ ] ¹²⁻ , [H ₂ P ₂ W ₁₂ O ^{_{48] 12-, [NaP 5 W}} 30 O 110] 14-, α- [SiW 9 O 34] 10-, γ- [SiW 10 O 36] 8-, α- [SiW 11 O 39 ^{_{8-, β- [SiW 11 O 39}} ] 8-, α- [PMo 12 O 40] 3-, α- [PW 11 MoO 40] 3-, α- [PW 9 Mo 3 O 40] 3-, α -[PW ₃ Mo ₉ O ₄₀ ] ³⁻ , α- [SiMo ₁₂ O ₄₀ ] ⁴⁻ , α- [P ₂ Mo ₁₈ O ₆₂ ] ^{6− and the} like.
The divalent or higher valent heteropolyacid anion containing one or more of molybdenum atom and tungsten atom is a heteropolyacid containing P (phosphorus atom) from the viewpoint of heat resistance and light resistance and easy availability of raw materials. More preferably.
The divalent or higher valent heteropolyacid anion containing one or more of molybdenum atoms and tungsten atoms can be used singly or in combination of two or more.

  When the heteropolyacid contains both molybdenum and tungsten, the molar ratio of molybdenum to tungsten is not particularly limited.

In the said general formula (I), a represents the valence of a heteropolyacid anion, and when a heteropolyacid anion of a different valence is used in combination, the average value is represented. The valence of the cation (A) is the average value of the cation (monovalent) represented by the general formula (II) and the cation (divalent) represented by the general formula (III). .
b and c each represent a number of 1 or more, and when the valence of the cation (A) satisfies a × c / b, the color material represented by the general formula (I) is a normal salt.

<The manufacturing method of the color material represented by general formula (I)>
The colorant represented by the general formula (I) includes, for example, one or more cations selected from the cation represented by the general formula (II) and the cation represented by the general formula (III), and a It can be obtained by mixing a valent heteropolyacid anion in a solvent and heating as necessary.

  The aminium cation and the diimonium cation can be synthesized with reference to, for example, the methods described in Japanese Patent No. 4942320, International Publication No. 2008/010501, etc. Moreover, you may use a commercial item.

[Colorant dispersion]
The color material dispersion according to the present invention comprises a color material represented by the following general formula (I), a dispersant, and a solvent having a solubility of the color material at 23 ° C. of 0.1 (mg / 10 g solvent) or less. It is characterized by containing.

(The symbols in general formula (I) are as described above.)

  The color material dispersion of the present invention is used by combining the color material represented by the general formula (I) and a dispersant and dispersing the color material in a solvent in which the color material is not substantially dissolved or a hardly soluble solvent. A colorant dispersion capable of forming a coating film excellent in heat resistance and light resistance while achieving the same high transmittance as that of the dye can be obtained.

The color material dispersion according to the present invention contains at least a color material, a dispersant, and a solvent, and may contain other components as necessary.
Hereinafter, each component of the color material dispersion liquid of the present invention will be described in detail in order. However, the color material represented by the general formula (I) is as described above, and the description thereof is omitted here. .

(Dispersant)
In the color material dispersion according to the present invention, the color material represented by the general formula (I) is used by being dispersed in a solvent. In the present invention, a dispersant is used in order to favorably disperse the color material. The dispersant can be appropriately selected from those conventionally used as pigment dispersants. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.

  Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes Long chain polyaminoamide phosphates; polyethylenimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxyls) Polyester, polyamide or ester-amide co-condensation with groups The reaction product obtained by reacting one or more compound selected from among the three compounds of (polyester amide)), and the like.

  Among the polymer dispersants, among them, the colorant represented by the above general formula (I) can be suitably dispersed, and the polymer dispersion containing a nitrogen atom in the main chain or side chain from the viewpoint of good dispersion stability Agents are preferred. When a polymer dispersant containing a nitrogen atom in the main chain or side chain is used, not only the colorant represented by the general formula (I) is well dispersed but also represented by the general formula (I). It is presumed that the coloring material also has an effect of stably existing in the state of ion pairs. As a result, it is excellent in heat resistance and light resistance.

Examples of the polymer dispersant containing a nitrogen atom in the main chain or side chain include (partial) amine salts, (partial) ammonium salts and (partial) of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid. Examples include alkylamine salts; polyurethanes; unsaturated polyamides; polyethyleneimine derivatives; polyallylamine derivatives.
Specific examples of the polymer dispersant containing a nitrogen atom in the main chain or side chain include those described in International Publication No. 2012/144521 pamphlet.

Examples of commercially available polymer dispersants containing a nitrogen atom in the main chain or side chain include the following.
Examples of (partial) amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid include Disperbyk 2000, 2001 (all manufactured by BYK Chemie). Can be used.
As the polyurethane, for example, Disperbyk 161 can be used.
As unsaturated polyamides, for example, Disperbyk 101 and 130 can be used.
As the polyallylamine derivative, for example, Azisper PB821, PB822, PB824, PB827 (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like can be used.
As the polyethyleneimine derivative, for example, Solsperse 33500 (manufactured by Nippon Lubrizol Co., Ltd.) can be used.
Other commercially available dispersants include Dysperbyk 116, 140, 160, 162, 163, 164, 166, 167, 168, 170, 171, 174, 182, and 2050. 6919 (manufactured by Big Chemie); EFKA 4046, 4047, (manufactured by EFKA CHEMICALS); Solsperse 12000, 13250, 13940, 17000, 20000, 24000GR, 24000SC, 27000, 28000, 32000, 33500, 35200, 37500 (above, manufactured by Nihon Lubrizol Corporation); Azisper PB711, 823, 880 (above, manufactured by Ajinomoto Fine Techno Co., Ltd.).

  Among polymer dispersants containing a nitrogen atom in the main chain or side chain, it may be a polymer having a structural unit represented by the following general formula (IV) from the viewpoint of the dispersibility and dispersion stability of the coloring material. Preferably, the amino group of the structural unit is a copolymer in which a salt is formed with one or more organic acid compounds selected from the following general formula (V) and the following general formula (VI). preferable.

(In General Formula (IV), R ⁹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, R ¹⁰ is an alkylene group having 1 to 8 carbon atoms, — [CH (R ¹⁴ ) —CH (R ¹⁵ ) —O] _x —CH (R ¹⁴ ) —CH (R ¹⁵ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — The groups R ¹¹ and R ¹² each independently represent a hydrogen atom or an optionally substituted chain or cyclic hydrocarbon group, or R ¹¹ and R ¹² are bonded to each other to form a cyclic structure. R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

(In General Formula (V) and General Formula (VI), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, Aralkyl group, aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″} R ^a and R ^{a ′} each contain ^a carbon atom, and R ^{a ″} is an alkyl group having 1 to 18 carbon atoms and an alkenyl group having 2 to 18 carbon atoms. , An aralkyl group, an aryl group, a monovalent group represented by — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e is there.
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R. ^e or a monovalent group represented by — [(CH ₂ ) _t —O] _u —R ^e .
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl Group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^f , and R ^f is a hydrogen atom. Or it is a C1-C5 alkyl group.
In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. )

  Examples of the divalent linking group Q in the general formula (IV) include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH— group, a —COO— group, and an ether group having 1 to 10 carbon atoms. (—R′—OR ″ —: R ′ and R ″ are each independently an alkylene group) and combinations thereof. Especially, it is preferable that Q is a -COO- group from the heat resistant point of the obtained copolymer.

The divalent organic group R ¹⁰ in the general formula (IV) is an alkylene group having 1 to 8 carbon atoms, — [CH (R ¹⁴ ) —CH (R ¹⁵ ) —O] _x —CH (R ¹⁴ ) —. CH (R ¹⁵ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y —. The alkylene group having 1 to 8 carbon atoms may be linear or branched, and includes, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, various types. Xylene group, various octylene groups and the like.
R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a methyl group.
R ¹⁰ is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility. Among them, R ¹⁰ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. An ethylene group is more preferable.

Examples of the cyclic structure formed by combining R ¹¹ and R ^{12 in} the general formula (IV) with each other include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. It is done. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring.

  Examples of the repeating unit represented by the general formula (IV) include (meth) acryloyloxypropyldimethylamine, (meth) acryloyloxyethyldimethylamine, (meth) acryloyloxypropyldiethylamine, (meth) acryloyloxyethyldiethylamine, and the like. Examples include, but are not limited to, derived repeating units.

In the general formula (V), when R ^a and / or R ^{a ′} is —O—R ^{a ″} , it is an acidic phosphate ester. In the general formula (VI), R ^b is —O—R ^{b ′.} In this case, it becomes an acidic sulfate ester.

As the organic acid compound represented by the general formula (V), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, or an aryl group which may have a substituent. Or an aralkyl group, a vinyl group, an allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , or — A monovalent group represented by O—R ^{a ″} , one of R ^a and R ^{a ′} contains a carbon atom, and R ^{a ″} has a methyl group, an ethyl group, and a substituent; Aryl group or aralkyl group, vinyl group, allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u — is R ^{e, R c} and ^{R d} are each independently a hydrogen atom or a methyl group, ^{R e} is -CO-CH = CH Or _{-CO-C (CH} 3) = ones is CH ₂ can improve the dispersibility of the colorant, and, from the viewpoint of excellent heat resistance.

Moreover, as an organic acid compound represented by general formula (VI), ^Rb is a methyl group, an ethyl group, the aryl group or aralkyl group which may have a substituent, a vinyl group, an allyl group,-[ ^{CH (R c) -CH (R} d) -O] s -R e, or _{- [(CH 2) t -O} ] u -R e, or a monovalent group represented by -O-R ^{b '} And R ^{b ′} is a methyl group, an ethyl group, an aryl group or an aralkyl group which may have a substituent, a vinyl group, an allyl group, — [CH (R ^c ) —CH (R ^d ) —O _S —R ^e or — [(CH ₂ ) _t —O] _u —R ^e , R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is —CO—CH═. Since CH ₂ or —CO—C (CH ₃ ) ═CH ₂ improves the dispersibility of the color material and is excellent in heat resistance. preferable.

Of these, organic acid compound represented by the above general formula (V) and the general formula ^{(VI), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' An aromatic ring is preferable from the viewpoint of improving the dispersibility of the coloring material and excellent heat resistance. At least one of R ^a , R ^{a ′} and R ^{a ″} , or R ^b or R ^{b ′} , an aryl group or aralkyl group which may have a substituent, more specifically, a benzyl group, A phenyl group, a tolyl group, a naphthyl group, and a biphenyl group are preferable from the viewpoint of dispersibility of the coloring material. In the general formula (V), when one of R ^a and R ^{a ′} has an aromatic ring, the other of R ^a and R ^{a ′} is preferably a hydrogen atom or a hydroxyl group.

In addition, from the viewpoint of heat resistance and chemical resistance, particularly alkali resistance, the organic acid compounds represented by the general formula (V) and the general formula (VI) include phosphorus (P), sulfur (S), and carbon. It is preferably a compound in which atoms are directly bonded, and R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aralkyl group. , An aryl group,-[CH (R ^c ) -CH (R ^d ) -O] _s -R ^e ,-[(CH ₂ ) _t -O] _u -R ^e , a monovalent group represented by R one of ^a and R ^{a 'preferably} contains carbon atoms. R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —. A monovalent group represented by R ^e , — [(CH ₂ ) _t —O] _u —R ^e is preferable.

The organic acid compound represented by the above general formula (V) and the general formula ^{(VI), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' Preferably have a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group including a cyclic ether-containing group such as an oxirane ring and an oxetane ring. Among these, a radical polymerizable group is preferable, and an ethylenically unsaturated bond-containing group is preferable. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, an allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O]. It is preferable that _u −R ^e and R ^e be —CO—CH═CH ₂ or —CO—C (CH ₃ ) ═CH ₂ , particularly R ^a , R ^{a ′} and / or R ^{a. ''} And / or R ^b and / or R ^{b ′} are preferably a vinyl group, an allyl group, a 2-methacryloyloxyethyl group, or a 2-acryloyloxyethyl group.

  In the present invention, the dispersant preferably further includes a structural unit having solvent affinity. Among them, from the viewpoint of improving solvent affinity and improving dispersibility, it may be used by appropriately selecting from repeating units derived from non-basic monomers according to the solvent so as to have solvent affinity. preferable. Here, the non-basic monomer gives a solution having a pH lower than 7.1 when dissolved in water at 25 ° C. at a concentration of 0.1 N (saturation concentration when the saturation concentration is less than 0.1 N). A polymerizable monomer. As a block part which has solvent affinity, the polymer of unsaturated carboxylic acid esters, such as polyacrylic acid ester, unsaturated carboxylic acid polymers, such as polyacrylic acid, etc. are mentioned, for example. Among these, a polymer having a repeating unit represented by the following general formula (V) is preferable from the viewpoint of improving heat resistance while improving dispersibility and dispersion stability of the coloring material.

(In General Formula (VII), R ¹⁶ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, R ¹⁷ is an alkyl group having 1 to 18 carbon atoms, and 2 to 18 carbon atoms. Alkenyl group, aralkyl group, aryl group, monovalent represented by — [CH (R ¹⁸ ) —CH (R ¹⁹ ) —O] _x —R ²⁰ or — [(CH ₂ ) _y —O] _z —R ²⁰ R ¹⁸ and R ¹⁹ are each independently a hydrogen atom or a methyl group, and R ²⁰ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms. , An aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ²¹ , wherein R ²¹ is a hydrogen atom or a linear or branched group having 1 to 5 carbon atoms. Or a cyclic alkyl group, where x is 1 to 1. (8 is an integer, y is an integer of 1 to 5, z is an integer of 1 to 18. m is an integer of 3 to 200, and n is an integer of 10 to 200.)

  A block copolymer having a block part having a structural unit represented by the general formula (II) and a block part having a structural unit represented by the general formula (V), and represented by the general formula (II) As specific examples of the graft copolymer having the structural unit, a block copolymer and a graft copolymer described in JP2013-76764A and the like can be preferably exemplified.

  In this invention, a dispersing agent can be used individually by 1 type or in combination of 2 or more types. Content of a dispersing agent is suitably selected according to the kind etc. of coloring material to be used. In the colorant dispersion of the present invention, the dispersant is usually in the range of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the colorant. It is more preferable that If the content is within the above range, the color material can be uniformly dispersed. Moreover, in the resin composition described later, a colored layer having sufficient hardness can be formed without relatively reducing the blending ratio of the binder component.

(solvent)
The solvent used in the present invention is a solvent that does not substantially dissolve the color material represented by the general formula (I) or a hardly soluble solvent, and the solubility of the color material at 23 ° C. is 0.1 (mg). / 10 g solvent) The following solvents. By using such a solvent, the color material dispersion according to the present invention can be used by dispersing the color material as particles (aggregates) in a solvent. The color material represented by the general formula (I) used in the present invention is excellent in heat resistance and light resistance by being dispersed in a solvent while maintaining its aggregation state. Among them, a solvent having a solubility of the coloring material at 23 ° C. of 0.01 (mg / 10 g solvent) or less is preferable, and a solvent that does not substantially dissolve the coloring material is more preferable.

In the present invention, a solvent having a colorant represented by the general formula (I) having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less can be simply determined by the following evaluation method. Can be determined.
Into a 20 mL sample tube, 10 g of the solvent to be evaluated is added, 0.1 g of the coloring material is further added, the lid is covered, shaken well for 20 seconds, and then allowed to stand in a 23 ° C. water bath for 10 minutes. 5 g of this supernatant liquid is filtered to remove insoluble matters. The absorbance spectrum of a solution obtained by further diluting the obtained filtrate 1000 times was measured with a UV-visible near-infrared spectrophotometer (for example, UV-3100PC manufactured by Shimadzu Corporation) using a 1 cm cell, and the absorbance at the maximum absorption wavelength was measured. Ask. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solvent has a colorant represented by the general formula (I) having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less. It can be evaluated that it is a solvent (slightly soluble solvent).

  Further, in the above evaluation method, an absorbance spectrum is measured in the same manner as above without diluting the obtained filtrate, and the absorbance at the maximum absorption wavelength is obtained. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solvent can be evaluated as a solvent that does not substantially dissolve the coloring material represented by the general formula (I).

  The solvent having a solubility of the coloring material at 23 ° C. of 0.1 (mg / 10 g solvent) or less may be a solvent that does not substantially dissolve the coloring material represented by the general formula (I) or a hardly soluble solvent. There is no particular limitation, and it does not react with each component in the colorant dispersion, and may be appropriately selected from solvents that can be dissolved or dispersed.

In the colorant dispersion of the present invention, it is particularly preferable to use an ester solvent from the viewpoint of dispersion stability.
Examples of the ester solvents include ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methoxyethyl acetate, pro, pyrene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl. Examples include acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate.

These solvents may be used alone or in combination of two or more.
The color material dispersion of the present invention is prepared by using the solvent as described above usually at a ratio of 60 to 85% by mass with respect to the total amount of the color material dispersion containing the solvent. When there are too few solvents, a viscosity will rise and a dispersibility will fall easily. Moreover, when there are too many solvents, color material density | concentration will fall and there exists a possibility that sufficient near-infrared absorption effect may not be acquired depending on a use.

(Other ingredients)
If necessary, the colorant dispersion of the present invention may further contain pigments, dyes, dispersion auxiliary resins, and other components.
The pigment and the dye are blended as necessary for the purpose of controlling the color tone. Conventionally known pigments and dyes can be selected according to the purpose, and can be used singly or in combination of two or more. The blending amount of the pigment and the dye is not particularly limited as long as the effect of the present invention is not impaired, and can be the same as that used in the resin composition described later.
Examples of the dispersion auxiliary resin include alkali-soluble resins. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, and may have the effect of stabilizing the dispersion or reducing the dispersant due to the dispersion stabilizing effect.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

<Method for producing colorant dispersion>
The colorant dispersion of the present invention is prepared by mixing and stirring the dispersant in the solvent to prepare a dispersant solution, and then adding the colorant according to the present invention and other compounds as necessary to the dispersant solution. Can be mixed and dispersed using a disperser. The color material dispersion of the present invention may be prepared by mixing a color material and a dispersant in a solvent and dispersing the mixture using a known disperser.

  Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibrating ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.10 to 1.0 mm.

  Specifically, preliminary dispersion is performed with 2 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a 0.1-0.5 micrometer membrane filter after dispersion | distribution.

In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited. However, the color material represented by the general formula (I) is refined to achieve high near infrared absorption. From the point of view, it is preferably set to 5 to 40 hours.
In this way, a color material dispersion excellent in dispersibility of the color material particles is obtained.

The average dispersed particle size in the colorant dispersion of the colorant used in the present invention is not particularly limited as long as it is appropriately set depending on the application, but is in the range of 10 to 150 nm from the viewpoint of excellent heat resistance and light resistance. Is preferably within the range of 20 to 125 nm. When the average dispersed particle diameter of the color material is in the above range, the surface coated with the color material dispersion of the present invention exhibits uniform and excellent infrared absorption performance.
The average dispersed particle size of the color material in the color material dispersion is a dispersed particle size of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is. The particle size can be measured with a laser light scattering particle size distribution meter by appropriately diluting the color material dispersion liquid to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times). Etc.) and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, a track particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is a volume average particle size.

  The color material dispersion can be used as a preliminary preparation for preparing a resin composition described later. That is, the colorant dispersion is a preliminarily prepared (colorant content mass in the composition) / (solid content mass other than the colorant in the composition) ratio in the pre-stage of preparing the resin composition described later. Is a high colorant dispersion. Specifically, the ratio of (mass of coloring material in composition) / (mass of solid content other than coloring material in composition) is usually 1.0 or more. By mixing the color material dispersion and at least the binder component, a resin composition having excellent dispersibility can be prepared.

[Resin composition]
The resin composition according to the present invention contains a colorant represented by the following general formula (I) and a binder component.

(The symbols in general formula (I) are as described above.)

The resin composition of the present invention can form a colored layer excellent in heat resistance and light resistance by using the color material of the present invention in combination with a binder component.
The resin composition of the present invention contains at least the colorant according to the present invention and a binder component, and may have other components as necessary.
Moreover, you may use the resin composition of this invention combining a binder component with the said color material dispersion liquid. In this case, the resin composition of the present invention has a colorant represented by the general formula (I), a binder component, a dispersant, and a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent). Contains the following solvents.
Hereinafter, each component of the resin composition of this invention is demonstrated in detail. The components that can be included in the color material dispersion according to the present invention can be the same as those described in the above-mentioned color material dispersion, and thus the description thereof is omitted here.

(Binder component)
In the present invention, the binder component contains at least a resin. The resin may be any of a thermoplastic resin, a thermosetting resin, and a photocurable resin.

  As thermoplastic resins, epoxy resins; acrylic resins such as polymethyl methacrylate and polyacrylic amide; polystyrene resins; cellulose resins such as nitrocellulose and ethyl cellulose; polyester resins; thermoplastic urethane resins; Preferred examples include modified olefin resins such as polyethylene and chlorinated polypropylene; vinyl resins such as vinyl acetate resins, vinyl chloride-vinyl acetate copolymers and butyral resins, and amorphous polyolefins having a norbornene structure. Among these, the glass transition temperature is preferably in the range of 90 to 180 ° C, particularly preferably in the range of 120 to 180 ° C.

In the present invention, a curable binder component containing a thermosetting resin or a photocurable resin is included in order to impart film formability and adhesion to the surface to be coated, and to impart sufficient hardness to the coating film. Is preferred. It does not specifically limit as a curable binder component, A conventionally well-known curable binder component can be used suitably.
Examples of the curable binder component include a photocurable binder component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a thermosetting resin that can be polymerized and cured by heating. What contains the thermosetting binder component to contain can be used.

  As the thermosetting binder, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst capable of promoting a thermosetting reaction may be added. Examples of the thermosetting functional group include an epoxy group, an oxetanyl group, an isocyanate group, and an ethylenically unsaturated bond. An epoxy group is preferably used as the thermosetting functional group. Specific examples of the thermosetting binder component include those described in International Publication No. 2012/144521 pamphlet.

On the other hand, when using a photolithography process when forming a colored layer, the photosensitive binder component which has alkali developability is used suitably.
Hereinafter, although the photosensitive binder component is demonstrated, a curable binder component is not limited to these.

(1) Photosensitive binder component Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. Examples of the positive photosensitive binder component include an alkali-soluble resin and a system containing an o-quinonediazide group-containing compound as a photosensitizing component, and examples of the alkali-soluble resin include a polyimide precursor.

  As the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used. Specific examples of the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator include those described in International Publication No. 2012/144521 pamphlet.

(Optional additive)
The resin composition of the present invention may contain other colorants and various additives as necessary within a range that does not impair the object of the present invention.

(Other color materials)
Other color materials are blended as needed for the purpose of controlling the color tone. Conventionally known color materials can be selected according to the purpose, and one or more color materials can be used.

(Additive)
Examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
Specific examples of the surfactant and the plasticizer include those described in International Publication No. 2012/144521 pamphlet.

(Mixing ratio of each component in the resin composition)
The total content of the coloring material represented by the general formula (I) and other coloring materials blended as necessary is 5 to 65% by mass, more preferably based on the total solid content of the resin composition. It is preferable to mix | blend in the ratio of 8-55 mass%. When there are too few coloring materials, there exists a possibility that it may become difficult to obtain desired infrared absorptivity. Also, if there are too many coloring materials, the properties as a coating film such as adhesion to the substrate when the resin composition is applied to the substrate and cured, surface roughness of the cured film, coating film hardness, etc. are insufficient. In addition, since the ratio of the amount of the dispersant used for dispersing the coloring material in the resin composition increases, characteristics such as solvent resistance may be insufficient. In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also contained.
Moreover, when using a dispersing agent, what is necessary is just to adjust suitably content of the said dispersing agent in the range which can disperse | distribute a coloring material uniformly. For example, it is preferable to use 10 to 150 parts by mass with respect to 100 parts by mass of the color material, more preferably 15 to 45 parts by mass with respect to 100 parts by mass of the color material, and a ratio of 15 to 40 parts by mass. It is even more preferable to blend with. Moreover, it is preferable that content of a dispersing agent exists in the range of 1-60 mass% with respect to the solid content whole quantity of a resin composition, and it is preferable to exist in the range of 5-50 mass% especially. When the content of the dispersant is less than 1% by mass with respect to the total solid content of the resin composition, it may be difficult to uniformly disperse the color material, and when the content exceeds 60% by mass. May cause a decrease in curability and developability.
The total content of the binder component is preferably 24 to 94% by mass and 40 to 90% by mass with respect to the total solid content of the resin composition.
Moreover, what is necessary is just to adjust the content suitably, when using a solvent from points, such as the dispersibility of a coloring material and the coating property of a resin composition. The solvent is usually preferably in the range of 65 to 95% by mass, and more preferably in the range of 75 to 88% by mass, based on the total amount of the resin composition containing the solvent.

(Manufacture of resin composition)
The method for producing the resin composition is not particularly limited. When preparing a resin composition using the colorant dispersion according to the present invention, for example, (1) In the solvent, the colorant dispersion according to the present invention, a binder component, and various additions used as desired (2) A binder component and various additive components used as desired are added to a solvent and mixed, and then the colorant dispersion according to the present invention is added thereto. In addition, there is a method of mixing.

  The resin composition according to the present invention can be used, for example, as an invisible printing ink or an infrared absorbing paint. Moreover, the colored layer formed using the resin composition which concerns on this invention can be used for various filter uses, such as an infrared rays absorption filter, a heat ray absorption filter, a band pass filter, for example.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

(Synthesis Example 1: Synthesis of diimonium compound)
1.1 g (10.2 mmol) of 1,4-phenylenediamine, 10 g of 4-bromo-N, N-diethylaniline, 4.56 g of sodium-tert-butoxide, 226 mg of tri-tert-butylphosphine, bis (dibenzylideneacetone) A mixed solution of 172 mg of palladium (0) and 110 ml of toluene was heated to 100 ° C. under a nitrogen stream and refluxed for 5 hours. After confirming the completion of the reaction by thin layer chromatography (TLC), the reaction mixture was cooled to room temperature, and 200 ml of water and 100 ml of toluene were added. Extraction with toluene, washing with water and brine, followed by drying over magnesium sulfate.
Under reduced pressure, the solvent was distilled off with a rotary evaporator, and the obtained solid was washed with ethyl acetate / normal hexane = 1/2 to obtain 5.7 g of a brown solid diimonium compound. (Yield 80%)

(Synthesis Example 2: Synthesis of chloride salt of diimonium compound (comparative colorant A))
5.7 g of the dimonium compound obtained in Synthesis Example 1 was dissolved in ethyl acetate / acetone = 2/1, an aqueous solution of 46 ml of water containing 3.0 g of ferric chloride was added, and the mixture was stirred at 50 ° C. for 4 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, the solvent was distilled off with a rotary evaporator under reduced pressure, and the resulting solid was washed with acetone to give a comparative colorant A (green solid 6.0 g) represented by the following chemical formula (1). Obtained. (Yield 95%)

(Synthesis Example 3: Synthesis of Color Material A)
2.0 g of the comparative color material A obtained in Synthesis Example 2 was added to water and dissolved by stirring while heating. Thereto, 80 ml of an aqueous solution containing 5.48 g of phosphotungstic acid n-hydrate (n = 25.6) was added dropwise. After completion of the reaction, the mixture was cooled to room temperature, and the precipitated solid was filtered and washed with water to obtain 5.6 g (yield 86%) of colorant A represented by the following chemical formula (2).

(Synthesis Example 4: Synthesis of Color Material B)
In Synthesis Example 3, a mixture of phosphotungstic acid n hydrate and phosphomolybdic acid n hydrate (n = 73.0) (70:30 (molar ratio)) was used instead of phosphotungstic acid n hydrate. A coloring material B represented by the following chemical formula (3) was obtained in the same manner as in Synthesis Example 3 except that it was used (yield 81%).

(Synthesis Example 5: Synthesis of Color Material C)
In Synthesis Example 4, except that the molar ratio of phosphotungstic acid n-hydrate to phosphomolybdic acid n-hydrate was 50/50, the same as in Synthesis Example 4, represented by the following chemical formula (4) Colorant C was obtained (yield 74%).

(Synthesis Example 6: Synthesis of Color Material D)
In Synthesis Example 3, a coloring material D represented by the following chemical formula (5) was prepared in the same manner as in Synthesis Example 3 except that phosphomolybdic acid n hydrate was used instead of phosphotungstic acid n hydrate. Obtained (yield 87%).

(Synthesis Example 7: Synthesis of Binder Resin A)
A reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 130 parts by mass of diethylene glycol ethyl methyl ether (abbreviated as EMDG) as a solvent, and the temperature was raised to 110 ° C. in a nitrogen atmosphere. Then, 32 parts by mass of methyl methacrylate, 22 parts by mass of cyclohexyl methacrylate, 24 parts by mass of methacrylic acid, 2 parts by mass of α, α′-azobisisobutyronitrile (abbreviation AIBN) as an initiator and n as a chain transfer agent -The mixture containing 4.5 mass parts of dodecyl mercaptan was dripped continuously over 1.5 hours, respectively.
Thereafter, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropping.
Next, while blowing air, 22 parts by mass of glycidyl methacrylate was added, the temperature was raised to 110 ° C., 0.2 parts by mass of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours. 44 mass% solid content) was obtained.
The obtained binder resin A had a mass average molecular weight Mw of 8,500 and an acid value of 85 mgKOH / g. The mass average molecular weight Mw was calculated by gel permeation chromatography (GPC) using polystyrene as a standard substance and THF as an eluent, and the acid value was measured according to JIS-K0070.

(Production Example 1: Preparation of colorant dispersion A)
As a colorant, 6.03 parts by mass of the colorant A of Synthesis Example 3 and 3.73 parts by mass (effective solid content) of a block copolymer containing a tertiary amino group (trade name: BYK-LPN6919, manufactured by BYK Chemie). 0.60 parts by mass), 0.76 parts by mass of phenylphosphinic acid, 4.60 parts by mass of binder resin A in Synthesis Example 3 (39.14 parts by mass of effective solid content), 84.91 parts by mass of PGMEA, and paint With a shaker (manufactured by Asada Tekko), dispersion was performed with 2 mm zirconia beads for 1 hour as a preliminary dispersion, and further with 0.1 mm zirconia beads as a main dispersion for 4 hours to obtain a colorant dispersion A.

(Production Example 2: Preparation of colorant dispersion B)
A color material dispersion B was obtained in the same manner as in Production Example 1 except that the color material was replaced with the color material B of Synthesis Example 4.

(Production Example 3: Preparation of colorant dispersion C)
A color material dispersion C was obtained in the same manner as in Production Example 1 except that the color material was replaced with the color material C of Synthesis Example 5.

(Production Example 4: Preparation of colorant dispersion D)
A color material dispersion D was obtained in the same manner as in Production Example 1 except that the color material was replaced with the color material D of Synthesis Example 6.

Example 1
25.68 parts by mass of the colorant dispersion A obtained in Production Example 1, 35.34 parts by mass of the following binder composition A, 38.54 parts by mass of PGMEA, 0.04 parts by mass of a surfactant R08MH (manufactured by DIC), silane coupling Agent KBM503 (manufactured by Shin-Etsu Silicone) (0.4 parts by mass) was added and mixed, and pressure filtration was performed to obtain colored resin composition A of Example 1.

<Binder composition A (solid content 40% by mass)>
Alkali-soluble resin (Binder resin A of Synthesis Example 3, solid content 44% by mass): 18.18 parts by mass5 to 6-functional acrylate monomer (trade name: Aronix M403, manufactured by Toagosei Co., Ltd.): 8.00 parts by mass Photopolymerization initiator: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF): 3.00 parts by mass / photosensitization Agent: 2,4 Diethylthioxanthone (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.): 1.00 parts by mass; Solvent: propylene glycol monomethyl ether acetate (PGMEA): 19.82 parts by mass

(Example 2)
A colored resin composition B was obtained in the same manner as in Example 1 except that the color material dispersion was replaced with the color material dispersion B of Production Example 2.

(Example 3)
A colored resin composition C was obtained in the same manner as in Example 1 except that the color material dispersion was changed to the color material dispersion C of Production Example 3.

Example 4
A colored resin composition was obtained in the same manner as in Example 1 except that the color material dispersion was replaced with the color material dispersion D of Production Example 4.

(Comparative Example 1)
To 99.5 parts by mass of a 10% solution obtained by dissolving polyhydroxyethyl methacrylate resin (PHEMA resin (Mw = 20000)) in methanol, 0.5 part by mass of the comparative colorant A obtained in Synthesis Example 2 was added and stirred for 30 minutes. Colorant solution E was obtained.
Next, in Example 1, a colored resin composition E of Comparative Example 1 was obtained in the same manner as Example 1 except that the color material solution E was used instead of the color material dispersion A.

(Comparative Example 2)
CIR-1085F (manufactured by Nippon Carlit Co., Ltd., diimonium dye (diimonium cation and bistrifluoromethylsulfonylimide anion) was added to 99.5 parts by mass of a 10% solution in which polymethyl methacrylate resin (PMMA resin (Mw = 3000)) was dissolved in PGMEA. ), Hereinafter referred to as comparative color material B.) 0.5 parts by mass was added and stirred for 30 minutes to obtain a color material solution F.
Next, in Example 1, a colored resin composition F of Comparative Example 2 was obtained in the same manner as Example 1 except that the color material solution F was used instead of the color material dispersion A.

(Evaluation)
<Heat resistance evaluation>
Color materials A to D and comparative color materials A and B were heated at 10 ° C./min with TG-DTA (DTG-60A manufactured by SHIMADZU) and heated to 600 ° C., respectively. As the heat resistance evaluation, the temperature when the weight was reduced by 5% was measured, and this was defined as the 5% weight reduction temperature. The results are shown in Table 1. It is evaluated that the higher the 5% weight loss temperature, the better the heat resistance.

<Optical performance evaluation, heat resistance evaluation>
The colored resin compositions obtained in each Example and Comparative Example were each coated on a glass substrate having a thickness of 0.7 mm (manufactured by Nippon Electric Glass, “OA-10G”) using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. Subsequently, it was set as the cured film by irradiating 40 mJ / cm < ² > of ultraviolet-rays using an ultrahigh pressure mercury lamp. The colored substrate having the above-mentioned coating film is post-baked at 150 ° C. for 30 minutes in a clean oven, and the absorbance of the obtained colored film is measured with “UV-3100” manufactured by SHIMADZU before and after the post-baking. did. Table 2 shows the absorbance at a wavelength of 550 nm and a wavelength of 900 nm.
The absorbance change rate before and after post-baking was calculated by the following formula.
Rate of change = absorbance after post-bake / absorbance before post-bake The closer the rate of change to 1, the better the heat resistance.

<Light resistance evaluation>
The colored resin compositions obtained in each Example and Comparative Example were applied on a glass substrate having a thickness of 0.7 mm (manufactured by Nippon Electric Glass, “OA-10G”) using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. Subsequently, the cured film was obtained by irradiating 40 mJ / cm < ² > of ultraviolet-rays using an ultrahigh pressure mercury lamp. Each of the colored substrates having the coating film is subjected to a illuminance at a wavelength of 420 nm using a xenon lamp (Atlas Co., Ltd., Ci4000 Weathermeter, inner filter: quartz, outer filter: soda lime & infrared absorption coating (CIRA)) at atmospheric pressure. Irradiation was performed at 1.2 W / m ² for 12 hours (equivalent to 50 kJ / m ² ). The absorbance of the coating film before and after light irradiation with a xenon lamp was measured using “UV-3100” manufactured by SHIMADZU. The results are shown in Table 3.
The absorbance change rate before and after the light irradiation was calculated by the following formula.
Rate of change = Absorbance after light irradiation / Absorbance before light irradiation The closer the rate of change to 1, the better the light resistance.

[Summary of results]
From the results of Table 1, the comparative colorant A, which is a diimonium chloride, had poor heat resistance. As shown in Tables 2 and 3, the coating film formed using the colored resin composition F of Comparative Example 1 using the comparative color material A is light having a wavelength of 550 nm by post-baking or light irradiation. Increased, and the absorbance of light having a wavelength of 900 nm decreased. As described above, it was revealed that the coating film of Comparative Example 1 was colored by reducing the infrared absorption effect by heat or light.
As shown in Table 1, the comparative color material B had good heat resistance even when compared with the color materials A to D. However, the coating film of Comparative Example 2 using the comparative color material B had poor heat resistance as compared with Examples 1 to 4 as shown in Table 2. This is presumably because the comparative color material B was dissolved in the solvent. Further, the coating film of Comparative Example 2 had poor light resistance as shown in Table 3.
Color materials A to D having a heteropolyacid anion were excellent in heat resistance of the color material itself. Moreover, it became clear that the coating film of Examples 1-4 using the said color materials AD is excellent in heat resistance and light resistance.

Claims (8)

A coloring material represented by the following general formula (I), a dispersant, and a solvent having a solubility of the coloring material at 23 ° C. of 0.1 (mg / 10 g solvent) or less,
A colorant dispersion, wherein the dispersant contains a polymer dispersant containing a nitrogen atom in the main chain or side chain .
(In general formula (I), A represents a cation containing at least one selected from the following general formula (II) and the following general formula (III), and X ^a- represents an a-valent heteropolyacid anion. a represents a number of 2 or more, and b and c represent a number of 1 or more.)
(In General Formula (II) and General Formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a substituent. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ are each independently bonded to each other to represent an alicyclic complex. A ring may be formed.) 2. The colorant dispersion according to claim 1 , wherein X ^a− is an a-valent heteropolyacid anion containing one or more selected from a molybdenum atom and a tungsten atom.   The dispersant is a polymer having a structural unit represented by the general formula (IV), and is selected from the amino group of the structural unit, the following general formula (V), and the following general formula (VI). The colorant dispersion according to claim 1 or 2, comprising a copolymer that may form a salt with one or more organic acid compounds.
(In the general formula (IV), R ⁹ Is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, R ¹⁰ Is an alkylene group having 1 to 8 carbon atoms, — [CH (R ¹⁴ ) -CH (R ¹⁵ -O] _x -CH (R ¹⁴ ) -CH (R ¹⁵ )-Or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y A divalent organic group represented by-, R ¹¹ And R ¹² Each independently represents a hydrogen atom or an optionally substituted chain or cyclic hydrocarbon group, or R ¹¹ And R ¹² Are bonded together to form a ring structure. R ¹⁴ And R ¹⁵ Are each independently a hydrogen atom or a methyl group.
  x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )
(In general formula (V) and general formula (VI), R ^a And R ^{a ’} Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, or — [CH (R ^c ) -CH (R ^d -O] _s -R ^e ,-[(CH ₂ ) _t -O] _u -R ^e Or -O-R ^{a "} A monovalent group represented by R ^a And R ^{a ’} Any of which contains a carbon atom. R ^{a "} Is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group,-[CH (R ^c ) -CH (R ^d -O] _s -R ^e ,-[(CH ₂ ) _t -O] _u -R ^e It is a monovalent group shown by these.
  R ^b Is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group,-[CH (R ^c ) -CH (R ^d -O] _s -R ^e ,-[(CH ₂ ) _t -O] _u -R ^e Or -O-R ^{b ’} It is a monovalent group shown by these. R ^{b ’} Is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group,-[CH (R ^c ) -CH (R ^d -O] _s -R ^e Or-[(CH ₂ ) _t -O] _u -R ^e It is a monovalent group shown by these.
  R ^c And R ^d Are each independently a hydrogen atom or a methyl group, and R ^e Is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ Or -CH ₂ COOR ^f A monovalent group represented by R ^f Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
R ^a , R ^{a ’} And R ^b In the above, each of the alkyl group, alkenyl group, aralkyl group and aryl group may have a substituent.
  s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ) Containing a colorant represented by the following general formula (I), a binder component, and a dispersant;
The resin composition in which the said dispersing agent contains the polymeric dispersing agent which contains a nitrogen atom in a principal chain or a side chain .
(In general formula (I), A represents a cation containing at least one selected from the following general formula (II) and the following general formula (III), and X ^a- represents an a-valent heteropolyacid anion. a represents a number of 2 or more, and b and c represent a number of 1 or more.)
(In General Formula (II) and General Formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a substituent. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ are each independently bonded to each other to represent an alicyclic complex. A ring may be formed.) The resin composition according to claim 4, wherein the X ^a− is an a-valent heteropolyacid anion containing one or more selected from a molybdenum atom and a tungsten atom.   The dispersant is a polymer having a structural unit represented by the general formula (IV), and is selected from the amino group of the structural unit, the following general formula (V), and the following general formula (VI). The resin composition according to claim 4 or 5, comprising a copolymer that may form a salt with one or more organic acid compounds.
(In the general formula (IV), R ⁹ Is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, R ¹⁰ Is an alkylene group having 1 to 8 carbon atoms, — [CH (R ¹⁴ ) -CH (R ¹⁵ -O] _x -CH (R ¹⁴ ) -CH (R ¹⁵ )-Or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y A divalent organic group represented by-, R ¹¹ And R ¹² Each independently represents a hydrogen atom or an optionally substituted chain or cyclic hydrocarbon group, or R ¹¹ And R ¹² Are bonded together to form a ring structure. R ¹⁴ And R ¹⁵ Are each independently a hydrogen atom or a methyl group.
  x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )
(In general formula (V) and general formula (VI), R ^a And R ^{a ’} Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, or — [CH (R ^c ) -CH (R ^d -O] _s -R ^e ,-[(CH ₂ ) _t -O] _u -R ^e Or -O-R ^{a "} A monovalent group represented by R ^a And R ^{a ’} Any of which contains a carbon atom. R ^{a "} Is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group,-[CH (R ^c ) -CH (R ^d -O] _s -R ^e ,-[(CH ₂ ) _t -O] _u -R ^e It is a monovalent group shown by these.
  R ^b Is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group,-[CH (R ^c ) -CH (R ^d -O] _s -R ^e ,-[(CH ₂ ) _t -O] _u -R ^e Or -O-R ^{b ’} It is a monovalent group shown by these. R ^{b ’} Is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group,-[CH (R ^c ) -CH (R ^d -O] _s -R ^e Or-[(CH ₂ ) _t -O] _u -R ^e It is a monovalent group shown by these.
  R ^c And R ^d Are each independently a hydrogen atom or a methyl group, and R ^e Is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ Or -CH ₂ COOR ^f A monovalent group represented by R ^f Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
R ^a , R ^{a ’} And R ^b In the above, each of the alkyl group, alkenyl group, aralkyl group and aryl group may have a substituent.
  s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ) A coloring material represented by the following general formula (I).
(In the general formula (I), A is the cation represented a cation comprising one or more selected from the following general formula (II) and Formula (III) in the table, but the following general formula (III) And may contain a cation represented by the following general formula (II), wherein X ^a- represents an a-valent heteropolyacid anion, a is a number of 2 or more, and b and c are a number of 1 or more. Represents.)
(In General Formula (II) and General Formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a substituent. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ are each independently bonded to each other to represent an alicyclic complex. A ring may be formed.) The colorant according to claim 7, wherein the ^Xa- is an a-valent heteropolyacid anion containing at least one selected from a molybdenum atom and a tungsten atom.