JP2005154478A - Coloring matter, ink, method for ink-jet recording, ink sheet, color toner and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink having a good hue and forming images having high fastness under various service conditions and environmental conditions. <P>SOLUTION: A coloring matter is represented by general formula (1) (wherein, A, B, A' and B' denote each independently an aryl group or a heterocyclic group; R<SP>1</SP>denotes a hydrogen atom or a monovalent group; Z<SB>1</SB>denotes an oxygen atom or an NR<SP>2</SP>; Z<SB>2</SB>denotes an oxygen atom or an NR<SP>3</SP>; R<SP>2</SP>and R<SP>3</SP>denote each a hydrogen atom or a monovalent group; X<SB>1</SB>and X<SB>2</SB>denote each a bivalent linking group; and n1 and n2 denotes each 0 or 1, with the proviso that at least one of A, B, A' and B' is a heterocyclic group and all thereof are heterocyclic groups when at least one of A, B, A' and B' is a pyridone ring). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel dye, ink, ink jet recording method, ink sheet, color toner, and color filter.

  In recent years, materials for forming color images have become mainstream as image recording materials. Specifically, ink jet recording materials, thermal transfer recording materials, electrophotographic recording materials, transfer type silver halide photosensitive materials. Materials, printing ink, recording pens, etc. are actively used. In addition, color filters are used to record and reproduce color images in image sensors such as CCDs in photographic equipment and LCDs and PDPs in displays. These color image recording materials and color filters use the three primary colors (dyes and pigments) of the so-called additive color mixture method and subtractive color mixture method to display or record full color images. The fact is that there is no fast-acting dye that has absorption characteristics that can realize the above-mentioned conditions and can withstand various use conditions and environmental conditions, and improvement is strongly desired.

  The dyes used in each of the above applications must have the following properties in common. That is, it has favorable absorption characteristics in terms of color reproducibility, fastness under the environmental conditions used, for example, light resistance, heat resistance, moisture resistance, resistance to oxidizing gases such as ozone, and other chemical fastness such as sulfurous acid gas The property is good. In particular, there is a strong demand for compounds that have a good yellow hue and are robust against light, wet heat, and active gases in the environment, especially oxidizing gases such as ozone.

An azo compound is known as a compound having a yellow hue. Patent Documents 1 to 3 disclose aryl / aryl bisazo dyes. Further, Patent Document 4 discloses a hetero-azo-hetero type bisazo compound, but does not describe the use as an ink. However, further development of dyes having excellent light fastness, wet heat fastness, and fastness to active gases in the environment (oxidizing gases such as NO _x and ozone, as well as SO _x ) and ink compositions using the same Is desired.
US Pat. No. 6,290,763 JP 2001-329194 A Japanese Patent Laid-Open No. 2002-3766 U.S. Pat. No. 4,083,688

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention provides 1) a novel dye having absorption characteristics excellent in color reproducibility as one of the three primary colors and sufficient fastness to light, heat, humidity, and active gases in the environment. 2) Ink for printing such as inkjet, ink sheet in thermal recording material, color toner for electrophotography, LCD, PDP and other displays that provide colored images and coloring materials with excellent hue and fastness Providing various colored compositions such as color filters used in image sensors such as CCDs, etc. 3) In particular, due to the use of the dye, it exhibits a good hue and is effective in light, wet heat, and active gases in the environment, especially ozone gas. To provide an ink for ink jet recording and an ink jet recording method capable of forming a highly robust image, and 4) for industrial, agricultural, medical, academic research, etc. And to provide a novel dye derivative having a specific structure that may be useful organic compounds or intermediates thereof to have.

The present inventors have conducted research on pyrazolylazo dye derivatives with the aim of developing a dye having good hue and fastness to light, ozone, and wet heat. As a result, the following general formula (1) having a specific dye structure is obtained. Based on this finding, the present inventors have completed the present invention. That is, the subject of this invention was achieved by the following means.
<1> A dye represented by the following general formula (1).

(In the formula, A and A ′ each independently represent an aryl group or a heterocyclic group, B and B ′ each independently represent an arylene group or a divalent heterocyclic group, and R ¹ represents a hydrogen atom. Or represents a monovalent group, Z ₁ represents an oxygen atom or —NR ² —, Z ₂ represents an oxygen atom or —NR ³ —, R ² and R ³ represent a hydrogen atom or a monovalent group, X ₁ and X ₂ each represent a divalent linking group, and n 1 and n 2 each represent 0 or 1, provided that at least one of A, B, A ′ and B ′ is a heterocyclic group, and A, B, When at least one of A ′ and B ′ is a pyridone ring, they are all heterocyclic groups).
<2> The dye according to <1>, wherein the dye represented by the general formula (1) is a dye compound represented by the following general formula (2).

(Wherein R ¹ , R ⁴ and R ⁶ represent a monovalent group, R ⁵ and R ⁷ represent —OR ⁸ or —NHR ⁸ , R ⁸ represents a hydrogen atom or a monovalent group, Ar 1 And Ar 2 represents an alkyl group, an aryl group or a heterocyclic group, B represents an arylene group or a divalent heterocyclic group, Z ₁ represents an oxygen atom or —NR ² —, Z ₂ represents an oxygen atom or —NR ^{2 3-} represents, R ² and R ³ represent a hydrogen atom or a monovalent group, X ₁ and X ₂ represent a divalent linking group, and n 1 and n 2 are 0 or 1.)
<3> The dye according to <2>, wherein the dye represented by the general formula (2) is a dye compound represented by the following general formula (3).

(Wherein R ¹ , R ⁴ and R ⁶ represent a monovalent group, Ar 1 and Ar 2 represent an alkyl group, an aryl group or a heterocyclic group, X ₁ and X ₂ represent a divalent linking group, n1 and n2 are 0 or 1.)
<4> An ink containing at least one dye according to any one of <1> to <3> in the previous period.
<5> An ink jet recording method comprising forming an image using the ink according to the above <4> on an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support.
<6> An ink sheet comprising the coloring matter represented by the general formulas (1) to (3).
<7> A color toner comprising the coloring matter represented by the general formulas (1) to (3).
<8> A color filter comprising a dye represented by the general formulas (1) to (3).
<9> A bisazo compound represented by the general formula (3).

  The dye of the present invention has an absorption characteristic with excellent color reproducibility as one of the three primary colors, and has sufficient fastness to light, heat, humidity, and active gases in the environment. In addition, this dye gives color images and coloring materials with excellent hue and fastness. Ink for printing such as inkjet, ink sheet in thermal recording material, color toner for electrophotography, LCD and PDP display and CCD It is suitable for various colored compositions such as color filters used in imaging devices such as dyeing liquids and dyeing solutions for dyeing various fibers. In particular, it is possible to realize an ink for ink jet recording and an ink jet recording method that can form an image having a good hue by using the coloring matter and having high fastness to light and an active gas in the environment, particularly ozone gas.

Hereinafter, the present invention will be described in detail.
[Azo dye]
The azo dye in the present invention (the compound of the present invention, sometimes referred to as the dye of the present invention) is preferably represented by the general formula (1). Hereinafter, the general formula (1) will be described in detail.

  The aryl group or arylene group represented by A, A ′, B and B ′ includes a substituted or unsubstituted aryl group or arylene group. The substituted or unsubstituted aryl group or arylene group is preferably an aryl group or arylene group having 6 to 30 carbon atoms. Examples of substituents include halogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups (may be in the form of salts) ), Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group , Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group (also in salt form) ), Alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups An example is a silyl group. This will be described in more detail below.

  The halogen atom represents a chlorine atom, a bromine atom, an iodine atom or the like, and the alkyl group includes a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent include the same substituents as the aryl group or arylene group. Of these, a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in the form of a salt) and a carboxyl group (may be in the form of a salt) are preferable. Examples of the alkyl group include methyl, ethyl, butyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl and 4-sulfobutyl.

  The cycloalkyl group includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a 5- to 6-membered ring, and more preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent include the same substituents as the aryl group or arylene group. Examples of the cycloalkyl group include cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl.

Aralkyl groups include substituted or unsubstituted aralkyl groups. As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable. Examples of the substituent include the same substituents as the aryl group or arylene group. Examples of the aralkyl include benzyl and 2-phenethyl.
An alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They preferably include C2-C30 substituted or unsubstituted alkenyl groups such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl and the like. I can do it.

The alkynyl group is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.
The aryl group is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl.
The heterocyclic group is a monovalent group in which one hydrogen atom has been removed from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably 3 to 30 carbon atoms. It is a 5- or 6-membered aromatic heterocyclic group. For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, morpholino.

  The alkoxy group includes a substituted or unsubstituted alkoxy group. The substituted or unsubstituted alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms. Examples of the substituent include the same substituents as the aryl group or arylene group. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. For example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy It is.
The silyloxy group is preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy and t-butyldimethylsilyloxy.
The heterocyclic oxy group is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, and examples thereof include 1-phenyltetrazol-5-oxy and 2-tetrahydropyranyloxy.

The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. For example, formyloxy, acetyloxy, pivaloyloxy , Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy.
The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. For example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di- n-octylaminocarbonyloxy and Nn-octylcarbamoyloxy.

The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, and n-octylcarbonyloxy.
The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy. is there.

The amino group is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted anilino group having 6 to 30 carbon atoms. For example, amino, methylamino, dimethylamino, anilino, N-methyl -Anilino, diphenylamino, hydroxyethylamino, carboxyethylamino.
The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. For example, formylamino, acetylamino, Pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino.

The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino. .
The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxy. Carbonylamino.
The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxy) phenoxycarbonylamino. It is.

The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino. It is.
The alkyl and arylsulfonylamino groups are preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms and substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenyl Sulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino.

The alkylthio group is a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio.
The arylthio group is a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio.
The heterocyclic thio group is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio and 1-phenyltetrazol-5-ylthio.

The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N- Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl.
The alkyl and arylsulfinyl groups are preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p- Methylphenylsulfinyl.
The alkyl and arylsulfonyl groups are preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl.

  The acyl group is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms. A heterocyclic carbonyl group bonded to a carbonyl group is preferable, and examples thereof include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, and 2-furylcarbonyl.

The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p- (t-butyl) phenoxycarbonyl. It is.
The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, and n-octadecyloxycarbonyl.
The carbamoyl group is preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms. For example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methyl Sulfonyl) carbamoyl.

The phosphino group is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, and methylphenoxyphosphino.
The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, and examples thereof include phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl.
The phosphinyloxy group is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.
The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, and examples thereof include dimethoxyphosphinylamino and dimethylaminophosphinylamino.
The silyl group is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, and examples thereof include trimethylsilyl, t-butyldimethylsilyl, and phenyldimethylsilyl.

  Among the substituents of the aryl group or arylene group, those having a hydrogen atom may be substituted with the above group by removing at least one of them. Examples of such a group include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specific examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

  The monovalent or divalent heterocyclic group represented by A, A ', B and B' is preferably a 5-membered or 6-membered ring group, which may further have a condensed ring. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. In the present invention, heterocyclic groups can be classified into type I and type II. Type I is known as an acidic nucleus, for example, 5-pyrazolone ring, 5-aminopyrazole ring, oxazolone ring, barbituric acid ring, pyridone ring, rhodanine ring, pyrazolidinedione ring, pyrazolopyridone ring And Meldrum's acid ring, and a 5-pyrazolone ring and a 5-aminopyrazole ring are preferable. Type II is known as a basic nucleus, such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. Can be mentioned. Among them, an aromatic heterocyclic group is preferable, and preferable examples thereof are exemplified in the same manner as described above. Examples include thiazole and thiadiazole. Most preferred is thiadiazole. They may have a substituent, and examples of the substituent are the same as those of the aryl group or arylene group described above.

  In A, A ', B and B', A and A 'or B and B' are preferably the same, and more preferably both are heterocycles. When both are heterocycles, it is preferred that one of A, A 'and B, B' is a type I heterocycle and the other is a type II. More preferably, A and A 'are I type and B and B' are II type combinations.

Examples of the monovalent group represented by R ¹ , R ² and R ³ include the substituents of the aryl group or arylene group described above. Further, R ¹ is preferably a group represented by OR ⁹ , SR ⁹ or NR ¹⁰ R ¹¹ . R ⁹ , R ¹⁰ and R ¹¹ may represent a hydrogen atom, an alkenyl group, an alkyl group, an aryl group or an aralkyl group, and R ¹⁰ and R ¹¹ may form a 5- or 6-membered ring via a nitrogen atom. These substituents may be substituted with the substituents mentioned for the aryl group or arylene group described above. R ² and R ³ are preferably a hydrogen atom, an alkenyl group, an alkyl group, an aryl group or an aralkyl group. The alkenyl group, alkyl group, aryl group and aralkyl group represented by R ¹ , R ² and R ³ are as defined above.
Z ₁ and Z ₂ are preferably —NR ² — and —NR ³ —, and R ² and R ³ are the same as described above, and more preferably —NH—.

The divalent linking groups represented by X ₁ and X ₂ in the general formula (1) are alkylene groups (eg, methylene, ethylene, propylene, butylene, pentylene), alkenylene groups (eg, ethenylene, propenylene), alkynylene. Groups (eg, ethynylene, propynylene), arylene groups (eg, phenylene, naphthylene), divalent heterocyclic groups (eg, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine 2, 4-diyl group, quinoxaline-2, 3-diyl group), —O—, —CO—, —NR— (wherein R is a hydrogen atom, alkyl group or aryl group), —S—, —SO ₂ —, —SO -Or a combination thereof is preferred.
The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R alkyl group or aryl group may have a substituent. Examples of the substituent are the same as those of the aryl group or the arylene group. The alkyl group and aryl group of R are as defined above.
More preferably, an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, -S-, -SO-, -SO _2- Or it is more preferable that it is a combination thereof.
The total number of carbon atoms in the divalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  In the general formula (1), n1 and n2 represent 0 or 1, and preferably 1 (a combination of n1 = 1 and n2 = 1 is more preferable).

  In the present invention, the dye represented by the general formula (2) or (3) is more preferable. A bisazo compound represented by the general formula (3) is particularly preferable.

General formulas (2) and (3) will be described in detail. R ¹ is the same as ^{R 1} in the general formula (1). B and B ′ are the same as B and B ′ in the general formula (1). The monovalent group represented by R ⁴ and R ⁶ has the same meaning as the monovalent group described above. The monovalent group represented by R ⁵ and R ⁷ has the same meaning as the monovalent group described above. R ⁵ and R ⁷ are preferably NH ₂ or OH (which may be a salt). Divalent linking group represented by X ₁ and X ₂ have the same meanings as the linking group represented by X ₁ and X ₂ in the general formula (1). The aryl group represented by Ar1 and Ar2 has the same meaning as described above. The heterocyclic group represented by Ar1 and Ar2 has the same meaning as the above-mentioned type II heterocyclic group. The alkyl group represented by Ar1 and Ar2 has the same meaning as described above.

In the present invention, when the compounds represented by the general formulas (1), (2) and (3) require hydrophilicity, it preferably has two or more hydrophilic groups in the molecule. It is more preferable to have 10 hydrophilic groups, and it is particularly preferable to have 3 to 6 hydrophilic groups. However, when water is not used as the medium, it does not have to be hydrophilic.
Any hydrophilic group may be used as long as it is an ionic dissociation group. Specifically, a sulfo group, a carboxyl group (including salts thereof), a hydroxyl group, a phosphono group (may be a salt), and the like. Can be mentioned. A sulfo group, a carboxyl group (including salts thereof) and a phosphono group are preferable, and a sulfo group and a carboxyl group (including salts thereof) are more preferable.
The dyes represented by the general formulas (1), (2) and (3) preferably have a maximum absorption wavelength (λmax) of 380 to 490 nm in H ₂ O from the viewpoint of color reproducibility, It is more preferable to have a λmax of 400 to 480 nm, and it is particularly preferable to have a λmax of 420 to 460 nm.

  Specific examples (illustrated dyes 1 to 39) of the dyes represented by the general formulas (1), (2) and (3) are shown below, but the dyes used in the present invention are limited to the following examples. It is not a thing.

The dye of the present invention can be synthesized by the following method. A method for synthesizing Dye 1 will be described as a representative example.

(Synthesis example)
A diazo solution was prepared using 1.9 g of compound (a), added to a mixed solution of 3 g of compound (b) and 30 ml of MeOH at 10 ° C. or lower, and stirred at room temperature for 2 hours. The precipitated crystals were filtered to obtain 4 g of compound (c).
To a mixture of 4 g of compound (c), 21 ml of H ₂ O, and 42 ml of EtOH, 2.1 g of NaSH was added and refluxed for 30 minutes, followed by concentration. The precipitated crystals were filtered to obtain 3.7 g of compound (d).
3.5 g of compound (d) was dissolved in 70 ml of H ₂ O, an acetone solution containing 0.64 g of cyanyl chloride was added at 10 ° C. or lower, and the mixture was further stirred at 40 ° C. for 2 hours. Thereafter, 1.8 g of morpholine was added, the mixture was stirred at 80 ° C. for 2 hours, and column chromatography was performed using Sephadex to obtain 1.2 g of Dye 1.
λmax 438.4 nm (H ₂ O), ε: 4.71 × 10 ⁴ (dm ³ .cm / mol)

Other dyes can be synthesized in the same manner. Table 1 shows λmax of typical dyes in H ₂ O.

Applications of the dye of the present invention include image recording materials for forming images, particularly color images. Specifically, the recording materials include inkjet recording materials described in detail below, thermal recording materials, and pressure sensitive materials. There are recording materials, recording materials using electrophotographic methods, transfer type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink jet recording materials, thermal recording materials, recording materials using electrophotography, An ink jet recording material is preferable.
It can also be applied to solid-state imaging devices such as CCDs, color filters for recording and reproducing color images used in displays such as LCDs and PDPs, and dyeing solutions for dyeing various fibers.
Furthermore, it can be applied as an organic compound useful for industrial, agricultural, medical, academic research or the like or an intermediate thereof.
The coloring matter of the present invention is used after adjusting physical properties such as solubility, dispersibility, and heat mobility suitable for the application with a substituent. Further, the coloring matter of the present invention can be used in a dissolved state, an emulsified dispersed state, or a solid dispersed state depending on the system used.

[ink]
The ink of the present invention means an ink containing at least one kind of the coloring matter of the present invention. The ink of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The ink of the present invention can be produced by using a lipophilic medium or an aqueous medium as a medium and dissolving and / or dispersing the dye of the present invention in the medium. Preferably, an aqueous medium is used. The ink of the present invention includes an ink composition excluding a medium. If necessary, other additives are contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When the oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

  The anti-drying agent is suitably used for the purpose of preventing clogging due to drying of the ink-jet ink at the nozzles used in the ink jet recording system.

  The anti-drying agent is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said drying inhibitor may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  The penetration enhancer is preferably used for the purpose of allowing ink jet ink to penetrate better into paper. Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. it can. If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print-through).

  The ultraviolet absorber is used for the purpose of improving image storage stability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-211141, Cinnamic acid compounds described in, for example, Kaihei 10-88106, JP-A-4-298503, 8-53427, 8-239368, 10-182621, JP-A-8- No. 501291, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  As the pH adjuster, a neutralizer (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the inkjet ink, the pH adjusting agent is preferably added so that the inkjet ink has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the inkjet ink of the present invention is preferably 20 to 60 mN / m. Furthermore, 25-45 mN / m is preferable. The viscosity of the inkjet ink of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

  When the compound of the present invention is dispersed in an aqueous medium, it contains a dye and an oil-soluble polymer as described in JP-A No. 11-286637, Japanese Patent Application Nos. 2000-78491, 2000-80259, and 2000-62370. The coloring matter of the present invention in which colored fine particles are dispersed in an aqueous medium or dissolved in a high-boiling organic solvent as in Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, 2000-203857 Is preferably dispersed in an aqueous medium. The specific method for dispersing the dye of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the aforementioned patent. it can. Alternatively, the azo dye may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high-pressure emulsification dispersion method (high-pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patents, the ink jet recording ink preparation method described above is disclosed in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used to prepare the ink for inkjet recording of the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol),

Glycol derivatives (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol Monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether),

Amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polarities Solvent (for example, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1 , 3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.

  The compound of the present invention is preferably contained in an amount of 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass in 100 parts by mass of the ink of the present invention. It is more preferable to contain 5-9 mass parts. Further, in the ink of the present invention, other pigments may be used in combination with the compound of the present invention. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

  The ink of the present invention can be used not only for monochromatic image formation but also for full color image formation. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Furthermore, in the ink of the present invention, other yellow dyes can be used simultaneously with the coloring matter of the present invention. Any applicable yellow dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components); Azomethine dyes having open chain active methylene compounds, etc .; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye species Examples thereof include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

  Any applicable magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. And dyes.

  Any applicable cyan dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components; for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes, oxonol dyes, Polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
Applicable black materials include bisazo, trisazo, tetraazo dyes, and carbon black dispersions.

[Inkjet recording method]
In the ink jet recording method of the present invention, energy is supplied to the ink of the present invention, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, 2 JP-A-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153789, JP-A-10-217473, JP-A-10-235995, Form images on inkjet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. described in JP-A-10-337947, JP-A-10-217597, and JP-A-10-337947 .

  In forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the image receiving material may be before, after, or simultaneously with the application of the colorant. Therefore, even if the addition place is in the image receiving paper, It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, the methods described in Japanese Patent Application Nos. 2000-363090, 2000-315231, 2000-354380, 2000-343944, 2000-268952, 2000-299465, 2000-299465, 2000-297365 are preferably used. it can.

Hereinafter, a recording paper and a recording film used for ink jet printing using the ink of the present invention will be described. The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheet may be used, and the thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m ² . The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, as the support, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, and the like. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
For the polymer mordant, JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,273,853, 4,282,305, It is described in each specification of the same No. 4450224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

  The water-proofing agent is effective in making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.

  Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine-based antioxidants, and benzotriazole-based ultraviolet absorbers such as benzophenone. Of these, zinc sulfate is particularly preferred.

  The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826. Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

  The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.

  As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

  Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-131668, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

  The ink of the present invention is not limited to an ink jet recording method, and is a known method, for example, a charge control method for ejecting ink using electrostatic attraction, a drop-on-demand method (pressure pulse) using vibration pressure of a piezo element. Method), an acoustic ink jet method in which an electrical signal is converted into an acoustic beam and applied to the ink and the ink is ejected using the radiation pressure, and a thermal ink jet method in which bubbles are formed by heating the ink and the generated pressure is used. Used for etc. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

[Color toner]
The content of the compound of the present invention in 100 parts by weight of the color toner of the present invention is not particularly limited, but it is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more and 20 parts by weight or less. It is more preferable to contain 2 to 10 parts by mass. In addition, the color toner of the present invention may be used in combination with other dyes together with the compound of the present invention.
As the binder resin for a color toner into which the coloring matter of the present invention is introduced, all commonly used binders can be used. Examples thereof include styrene resin, acrylic resin, styrene / acrylic resin, and polyester resin.
Inorganic fine powders and organic fine particles may be externally added to the toner for the purpose of improving fluidity and controlling charging. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These have a number average primary particle diameter of preferably 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.

  As the release agent, all conventionally used release agents can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.

  The charge control agent may be added as necessary, but is preferably colorless from the viewpoint of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

  As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin-coated carrier whose magnetic material particle surface is coated with a resin or the like may be used. The average particle size of the carrier is preferably 30 to 150 μm in terms of volume average particle size.

  The image forming method to which the toner of the present invention is applied is not particularly limited. For example, a method of forming a color image after repeatedly forming a color image on a photoconductor to form an image, or a method of forming an image on a photoconductor. For example, the image may be transferred to an intermediate transfer member and the like, and a color image may be formed on the intermediate transfer member and then transferred to an image forming member such as paper to form a color image.

[Thermal transfer material]
The heat-sensitive recording material is composed of an ink sheet in which the dye of the present invention is coated on a support together with a binder, and an image receiving sheet that fixes the dye transferred in response to the thermal energy applied from the thermal head according to the image recording signal. Is done. The ink sheet is prepared by dissolving the compound of the present invention in a solvent together with a binder, or by dispersing in fine particles in a solvent, coating the ink on a support, and drying appropriately. Can be formed. The amount of ink applied on the support is not particularly limited, but is preferably 30 to 1000 mg / m ² . As the preferred binder resin, ink solvent, support, and image receiving sheet, those described in JP-A-7-137466 can be applied.

  In order to apply the heat-sensitive recording material to a heat-sensitive recording material capable of full-color image recording, a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image, and heat diffusion capable of forming a magenta image. It is preferable to form a magenta ink sheet containing a reactive magenta dye and a yellow ink sheet containing a heat diffusible yellow dye capable of forming a yellow image by sequentially coating the support. In addition, an ink sheet containing a black image forming substance may be further formed as necessary.

[Color filter]
As a color filter forming method, a pattern is first formed with a photoresist and then dyed, or disclosed in JP-A-4-163552, JP-A-4-128703, and JP-A-4-175753. Thus, there is a method of forming a pattern with a photoresist to which a dye is added. Any of these methods may be used as a method used when introducing the dye of the present invention into a color filter. Preferred methods are described in JP-A-4-175753 and JP-A-6-35182. The positive resist composition comprising a thermosetting resin, a quinonediazide compound, a cross-linking agent, a dye and a solvent, and after coating on a substrate, exposing through a mask and developing the exposed portion. Then, a positive resist pattern is formed, the positive resist pattern is exposed on the entire surface, and then the exposed positive resist pattern is cured, and a color filter forming method can be mentioned. In addition, a black matrix can be formed according to a conventional method to obtain an RGB primary color system or Y, MC complementary color system color filter. Although the usage-amount of the pigment | dye in a color filter is not restrict | limited in particular, 0.1-50 mass% is preferable.

  About the said thermosetting resin, a quinonediazide compound, a crosslinking agent, a solvent, and those usage-amounts, the thing as described in the said patent can be used preferably.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
After adding deionized water to the following components to make 1 liter, the mixture was stirred for 1 hour while being heated at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / L, and vacuum filtration was performed with a microfilter having an average pore diameter of 0.25 μm to prepare ink liquid A for yellow. The viscosity of the ink liquid A was 4.1 mPa · S, and the surface tension was 31 mN / m.

[Composition of ink liquid A]
Yellow dye of the present invention 15g
Diethylene glycol 20g
Glycerin 120g
Diethylene glycol monobutyl ether 230g
2-pyrrolidone 80g
Triethanolamine 17.9g
Benzotriazole 0.06g
Surfynol TG 8.5g
PROXEL XL2 (made by Zenaca) 1.8g

Ink liquids B and C were prepared in the same manner as the ink liquid A, except that the dye was changed as shown in Table 2 below.
At this time, ink liquids 101 and 102 were prepared using comparative dyes A and B in Table 2 as comparative ink liquids. The pH, viscosity and surface tension of the ink liquids B, C, 101 and 102 were substantially the same as the ink liquid A.
When changing the dye, it was used so that the added amount of the dye was equimolar with respect to the ink liquid A.

(Image recording and evaluation)
The following evaluations were performed on the inkjet inks of the above Examples (Ink Liquids A to C) and Comparative Examples (Ink Liquids 101 and 102). The results are shown in Table 2.
In Table 2, “color tone” and “water resistance” indicate that each ink-jet ink is photo glossy paper (PMSON paper manufactured by EPSON <gloss>) with an ink jet printer (manufactured by EPSON Corporation; PM-700C). (KA420PSK, EPSON) was printed by inkjet so as to have a density (reflection density) of 1.0, and it was tested.

<Color tone>
The color tone was visually evaluated in three stages: A (best), B (good), and C (poor). The value of λmax with PM photographic paper is also shown.

<Water resistance>
The photo glossy paper on which the image was formed was dried at room temperature for 1 hour, then dipped in deionized water for 10 seconds, naturally dried at room temperature, and the bleeding was visually observed. The evaluation was made in three stages, with A indicating low bleeding, B indicating moderate bleeding, and C indicating high bleeding.

<Light resistance>
The photo glossy paper on which the image is formed is irradiated with xenon light (85000 lx) for 7 days using a weather meter (Atlas C.I65), and the image density before and after the xenon irradiation is measured using a reflection densitometer (X-Rite310TR). And measured as a dye residual ratio. The reflection density before xenon irradiation was measured at three points of 1, 1.5 and 2.0.
The evaluation was made in three stages, with A being a dye residual ratio of 70% or more at any concentration, A being 1 or 2 points being less than 70% B, and C being less than 70% at all concentrations.

<Ozone resistance>
The photo glossy paper on which the image has been formed is left in a box set at an ozone gas concentration of 0.5 ± 0.1 ppm, room temperature and dark place for 7 days, and the image density before and after being left under ozone gas is measured by a reflection densitometer (X -Rite310TR) and evaluated as a dye residual ratio. The reflection density before standing in ozone gas was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The evaluation was made in three stages, with A being a dye residual ratio of 70% or more at any concentration, A being 1 or 2 points being less than 70% B, and C being less than 70% at all concentrations.

  As is clear from Table 2, the ink-jet ink of the present invention was excellent in color tone and excellent in water resistance, light resistance and ozone resistance. In particular, it is clear that the image storage stability such as light resistance and ozone resistance is excellent.

Example 2
The same ink produced in Example 1 was printed on an inkjet paper photo glossy paper EX manufactured by Fuji Photo Film using the same machine as in Example 1, and the same evaluation as in Example 1 was performed. Results were obtained.

Example 3
The same ink produced in Example 1 is packed in a cartridge of an inkjet printer BJ-F850 (manufactured by CANON), and an image is printed on the photo glossy paper GP-301 of the same printer, and the same evaluation as in Example 1 is performed. As a result, the same results as in Example 1 were obtained.

Example 4
(Preparation of ink liquid D)
2.5 g of the dye 18 of the present invention, 7.04 g of sodium dioctylsulfosuccinate in 4.22 g of the following high boiling organic solvent (s-2), 5.63 g of the following high boiling organic solvent (s-11) and 50 ml of ethyl acetate Was dissolved at 70 ° C. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse particle dispersion was micronized by passing it through a microfluidizer (MICROFLUIDEX INC) five times at a pressure of 600 bar. Further, the resulting emulsion was desolvated with a rotary evaporator until the odor of ethyl acetate disappeared. Ink D was prepared by adding 140 g of diethylene glycol, 50 g of glycerol, 7 g of SURFYNOL 465 (Air Products & Chemicals) and 900 ml of deionized water to the fine emulsion of the hydrophobic dye thus obtained. The physical properties of this ink were as follows: pH 8.5, viscosity 4.1 mPa · S, surface tension 33 mN / m.

(Preparation of ink liquid 103)
Ink liquid 103 was prepared in the same manner as ink liquid D, except that the dye of the present invention in ink liquid D was changed to an equimolar amount of the comparative dye shown in Table 3 below. The pH, viscosity, and surface tension of the ink liquid were substantially the same as those of the ink liquid D.

(Image recording and evaluation)
The following evaluation was performed on the ink liquid D and the comparative ink liquid 103. The results are shown in Table 3 below. In Table 3, the contents of “color tone (λmax)”, “water resistance”, “light resistance”, and “ozone gas resistance” are the same as those described in Example 1.

  As is apparent from Table 3, the ink-jet ink of the present invention was excellent in color developability and color tone, and excellent in water resistance and light resistance.

Example 5
The same ink prepared in Example 4 was printed on Fuji Photo Film inkjet paper photo glossy paper EX using the same machine of Example 4, and the same evaluation as in Example 4 was performed. Results were obtained.

Example 6
The same ink produced in Example 4 is packed into a cartridge of an inkjet printer BJ-F850 (manufactured by CANON), an image is printed on the company's photo glossy paper GP-301, and the same evaluation as in Example 4 is performed. As a result, the same result as in Example 4 was obtained.

Example 7
3 parts by mass of the dye 14 of the present invention, 100 parts by mass of a resin for toner [styrene-acrylic acid ester copolymer; trade name Hymer TB-1000F (manufactured by Sanyo Kasei)] are mixed and ground by a ball mill and heated to 150 ° C. After melt mixing, the mixture was cooled and coarsely pulverized with a hammer mill, and then finely pulverized with an air jet type pulverizer. Further, classification was performed to select 1 to 20 micron, and a toner was obtained. To 10 parts of this toner, 900 parts by mass of carrier iron powder (trade name: EFV250 / 400; manufactured by Nippon Iron Powder) was uniformly mixed to obtain a developer. Similarly, samples were prepared in the same manner except that 3 parts by weight of the dye and 6 parts by weight of the pigment were used as the colorant shown in Table 4. Using these developers, copying was performed with a dry plain paper electrophotographic copying machine [trade name NP-5000; manufactured by Canon Inc.].

In the evaluation test, a reflection image (an image on paper) and a transmission image (an OHP image) were produced on the paper and the OHP, respectively, by the above image forming method using the developer using the color toner of the present invention, and the following method was used. Carried out. The toner adhesion amount was evaluated in the range of 0.7 ± 0.05 (mg / cm ² ).

  The obtained image was evaluated for hue and light fastness. The hue was visually evaluated in three stages: best, good and poor. The evaluation results are shown in Table 4 below. In Table 4 below, A indicates the best hue; B indicates that the hue is good, and C indicates that the hue is poor. Regarding the light fastness, after measuring the image density Ci immediately after recording, the image was irradiated with xenon light (85,000 lux) for 5 days using a weather meter (Atlas C.165), and the image was again displayed. The density Cf was measured, and the dye residual ratio ({(Ci−Cf) / Ci} × 100%) was calculated from the difference in image density before and after the xenon light irradiation and evaluated. The image density was measured using a reflection densitometer (X-Rite 310TR). In addition, the said reflection density before xenon irradiation measured about the point of 1.0. The evaluation results are shown in Table 4 below. In Table 4 below, the case where the dye residual ratio is 90% or more is shown as A, the case where it is 90-80% is shown as B, and the case where it is less than 80% is shown as C.

  The transparency of the OHP image was evaluated by the following method. The visible spectral transmittance of an image is measured with a “330 type self-recording spectrophotometer” manufactured by Hitachi, Ltd., using an OHP sheet on which toner is not supported as a reference, the spectral transmittance at 650 nm is obtained, and the transparency of the OHP image is measured. It was. Spectral transmittance of 80% or more was A, 70 to 80% was B, and 70% or less was C. The results are shown in Table 4.

  As is apparent from Table 4, since the faithful color reproduction and high OHP quality are exhibited by using the color toner of the present invention, the color toner of the present invention is suitable for use as a full color toner. Furthermore, since the light resistance is good, an image that can be stored for a long time can be provided.

Example 8
<Preparation of thermal transfer dye donating material>
A 6 μm thick polyethylene terephthalate film (manufactured by Teijin) with a heat-resistant slip treatment on the back side is used as a support, and the coating composition for the thermal transfer dye donating layer having the following composition is dried on the surface of the film by wire bar coating. The thermal transfer dye-donating material (5-1) was prepared by coating so that the thickness at that time was 1.5 μm.
Thermal transfer dye-donating layer coating composition:
Dye 14 10mmol Polyvinyl butyral resin (Denkabutyral 5000-A manufactured by Electrochemicals) 3g
Toluene 40ml
Methyl ethyl ketone 40ml
Polyisocyanate (Takenate D110N, Takeda Pharmaceutical) 0.2ml
Next, a thermal transfer dye-donating material of the present invention and a comparative thermal transfer dye-donating material (5-2) were prepared in the same manner as described above except that the dye 14 was changed to the comparative dye described in Table 5.

(Creation of thermal transfer image receiving material)
Using a 150 μm thick synthetic paper (YUPO-FPG-150 manufactured by Oji Oil) as a support, the following composition is applied to the surface by wire bar coating so that the thickness when dried is 8 μm, and a thermal transfer image receiving material is obtained. Produced. Drying was performed for 30 minutes in an oven at a temperature of 100 ° C. after provisional drying with a dryer.
Image-receiving layer coating composition:
Polyester resin (Toyobo's Byron-280) 22g
Polyisocyanate (Dainippon Ink Chemical KP-90) 4g
Amino-modified silicone oil (Shin-Etsu Silicone KF-857) 0.5g
Methyl ethyl ketone 85ml
Toluene 85ml
Cyclohexanone 15ml

  The thermal transfer dye-donating material (5-1), (5-2) and the thermal transfer image-receiving material obtained as described above are superposed so that the thermal transfer dye-donating layer and the image-receiving layer are in contact with each other, and the thermal transfer dye-donating material is obtained. Using a thermal head from the support side, printing was performed under the conditions of an output of the thermal head of 0.25 W / dot, a pulse width of 0.15 to 15 milliseconds, and a dot density of 6 dots / mm, and the yellow on the image receiving layer of the image receiving material Colored dyes were dyed imagewise. Table 5 shows the maximum color density of the obtained image. With the thermal transfer dye donating material (5-1) of the present invention, a clear image recording without transfer unevenness was obtained. Next, each recorded thermal transfer image-receiving material obtained as described above was irradiated with Xe light (17000 lux) for 5 days to examine the light stability of the color image. The status A reflection density after irradiation of the portion showing the status A reflection density 1.0 was measured, and the stability was evaluated by the residual ratio (percentage) with respect to the reflection density 1.0 before irradiation. The results are shown in Table 5.

  As described above, the coloring matter of the present invention was excellent in light fastness as compared with the comparative dye. The hue was also fresh.

Example 9
Regarding the method for producing a color filter, a silicon wafer is spin-coated with a positive resist composition containing a thermosetting resin, a quinonediazide compound, a crosslinking agent, a dye and a solvent, and the solvent is evaporated by heating, and then exposed through a mask. The quinonediazide compound was decomposed. If necessary, a mosaic pattern was obtained by developing after heating. The exposure was performed with an i-line exposure stepper HITACHI LD-5010-i (NA = 0.40) manufactured by Hitachi, Ltd. The developer used was SOPD or SOPD-B manufactured by Sumitomo Chemical Co., Ltd.
<Preparation of positive resist composition>
Cresol novolak resin (polystyrene equivalent weight average molecular weight 4300) obtained from a m-cresol / p-cresol / formaldehyde (reaction molar ratio = 5/5 / 7.5) mixture 3.4 parts by mass, the following formula

O-Naphthoquinonediazide-5-sulfonic acid ester (average of two hydroxyl groups esterified) 1.8 parts by mass, hexamethoxymethylolated melamine 0.8 parts by mass, ethyl lactate 20 A positive resist composition was obtained by mixing 1 part by mass of the dye of the present invention shown in Table 6 with part by mass.
<Preparation of color filter>
The obtained positive resist composition was spin-coated on a silicon wafer, and then the solvent was evaporated. After the silicon wafer was exposed, it was heated at 100 ° C., and then the exposed portion was removed by alkali development to obtain a positive colored pattern having a resolution of 0.8 μm. This was exposed to light and heated at 150 ° C. for 15 minutes to obtain a yellow complementary color filter.

<Comparative example>
Instead of the yellow dye of the present invention used in the above examples, 1 part by mass of Oreosol Yellow 2G manufactured by Sumitomo Chemical Co., Ltd. was mixed to obtain a positive resist composition. After this positive resist composition was spin coated on a silicon wafer, the solvent was evaporated. After the silicon wafer was exposed, it was alkali-developed to obtain a positive colored pattern having a resolution of 1 μm. After the entire surface was exposed, it was heated at 150 ° C. for 10 minutes to obtain a yellow color filter.
<Evaluation / Test>
The transmission spectrum of the obtained yellow color filter was measured, and the short-wave side and long-wave side cuts of the spectrum important for color reproduction were relatively evaluated. A is good, B is somehow acceptable level, and C is some unacceptable level. Further, using a weather meter (Atlas C.I65), xenon light (85000 lx) was irradiated for 7 days, and the image density before and after the xenon irradiation was measured and evaluated as a dye residual ratio. In addition, the said reflection density before xenon irradiation measured about the point of 1.0.

  Compared with the comparative example, it can be seen that the dye of the present invention has sharp cuts on the short-wave side and long-wave side of the spectrum and is excellent in color reproducibility. It was also found that the light fastness was superior to the comparative compound.

Claims (8)

The pigment | dye represented by following General formula (1).

(In the formula, A and A ′ each independently represent an aryl group or a heterocyclic group, B and B ′ each independently represent an arylene group or a divalent heterocyclic group, and R ¹ represents a hydrogen atom. Or represents a monovalent group, Z ₁ represents an oxygen atom or —NR ² —, Z ₂ represents an oxygen atom or —NR ³ —, R ² and R ³ represent a hydrogen atom or a monovalent group, X ₁ and X ₂ each represent a divalent linking group, and n 1 and n 2 each represent 0 or 1, provided that at least one of A, B, A ′ and B ′ is a heterocyclic group, and A, B, When at least one of A ′ and B ′ is a pyridone ring, all are heterocyclic groups.) The dye according to claim 1, wherein the general formula (1) is represented by the following general formula (2).

(Wherein R ¹ , R ⁴ and R ⁶ represent a monovalent group, R ⁵ and R ⁷ represent —OR ⁸ or —NHR ⁸ , R ⁸ represents a hydrogen atom or a monovalent group, Ar 1 And Ar2 represents an alkyl group, an aryl group or a heterocyclic group, B and B ′ each independently represent an arylene group or a divalent heterocyclic group, Z ₁ represents an oxygen atom or —NR ² —, Z ₂ represents an oxygen atom or —NR ³ —, R ² and R ³ represent a hydrogen atom or a monovalent group, X ₁ and X ₂ represent a divalent linking group, and n 1 and n 2 represent 0 or 1 .) The dye according to claim 2, wherein the general formula (2) is represented by the following general formula (3).

(Wherein R ¹ , R ⁴ and R ⁶ represent a monovalent group, Ar 1 and Ar 2 represent an alkyl group, an aryl group or a heterocyclic group, X ₁ and X ₂ represent a divalent linking group, n1 and n2 are 0 or 1.)   An ink containing at least one pigment according to any one of claims 1 to 3.   An ink jet recording method for forming an image using an ink according to claim 4 on an image receiving material having an ink receiving layer containing white inorganic pigment particles on a support.   An ink sheet containing at least one pigment according to any one of claims 1 to 3.   A color toner containing at least one pigment according to any one of claims 1 to 3.   A color filter containing at least one pigment according to any one of claims 1 to 3.