CN100590151C - Dye, ink, inkjet recording method, ink sheet, toner and color filter - Google Patents

Abstract

To provide a dye with a good tone, which can form an image showing high fastness under various usage conditions and environmental conditions, said dye is especially suitable for ink, and the dye is represented by the formula (1): wherein R ₁ and R ₂ each independently represent a monovalent group, Z represents a nitrogen atom or a carbon atom bonded to a hydrogen atom or a monovalent group, and M represents a hydrogen atom or a cation, provided that the dye has two azo groups.

Description

Dye, ink, inkjet recording method, ink sheet, toner and color filter

technical field

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

Background technique

In recent years, image recording materials are mainly materials for forming color images, and more specifically, inkjet recording materials, heat transfer recording materials, electrophotographic recording materials, transfer process silver halide photosensitive materials, Printing ink and stylus. Also, color filters for recording or reproducing color images have been used in imaging devices such as CCDs in the field of photographic equipment or LCDs or PDPs in the field of displays. In these color image recording materials or color filters, in order to display or record full-color images, trichromatic dyes (dye or pigment) based on additive color mixing or subtractive color processes are used. However, it is a fact that there are no colorfast dyes that have absorption characteristics capable of realizing a superior color reproduction region and are resistant to various usage conditions and environmental conditions, and thus improvements in dyes are urgently needed.

The dyes for the above purposes are generally required to have the following properties. That is, they are required to have superior absorption characteristics in color reproduction, robustness to environmental conditions in which they are used, such as light fastness, heat resistance, moisture resistance, resistance to oxidizing gases such as ozone, and resistance to chemical substances such as Resistance to sulfurous acid gas and provides inks with excellent storage stability. Therefore, dyes having good yellow hue, good light fastness, good heat and humidity resistance and good resistance to reactive gases contained in the environment, and excellent storage stability are urgently needed.

As the yellow dye skeleton in the ink used for inkjet recording, there are typically azo-based dyes. As a typical example of an azo dye, a fast dye having a triazinylpyrazole skeleton is described in JP-A-2003-277662. However, dyes that provide more excellent storage stability are desired.

Contents of the invention

The object of the present invention is to solve the problems that conventional dyes have and to achieve the following objects. That is, the object of the present invention is to provide 1) a dye which has excellent color reproducibility as a dye of a three-color system, has sufficient light fastness, heat resistance, moisture resistance and environmental active gas resistance, and is effective in inks. exhibiting excellent storage stability, 2) various coloring compositions capable of providing color images or coloring materials excellent in tone and fastness, such as printing inks for inkjet printing, ink flakes in thermal recording materials, A toner for electrophotography and a color filter used in a display such as LCD or PDP or an image forming apparatus such as a CCD, and 3) particularly, an ink for an inkjet recording method and inkjet recording, which have excellent storage stability and good color tone, and it can form images with high light resistance, heat resistance, humidity resistance and environmental active gas resistance, especially resistance to ozone gas.

For the purpose of finding a dye that can provide an ink that exhibits good storage stability, exhibits good color tone, and has high light fastness, ozone fastness, heat resistance, and humidity resistance, the present inventors have studied pyrazolyl azo dye derivatives in detail, and as a result It was found that a compound represented by the following formula (1) can solve the above-mentioned problems, and thus completed the present invention. The means for solving the above-mentioned problems are as follows.

1. A dye represented by formula (1):

Wherein R _and R _each independently represent a monovalent group, Z represents a nitrogen atom or a carbon atom connected to a hydrogen atom or a monovalent group, M represents a hydrogen atom or a cation,

The proviso is that the dye has two azo groups.

2. The dye according to item 1, wherein the dye represented by formula (1) is the dye represented by formula (2):

wherein _R3 and _R4 each independently represent a monovalent group, _Ar1 and _Ar2 each independently represent an aryl group or a heterocyclic group, and M represents a hydrogen atom or a cation.

3. The dyestuff according to item 2, wherein Ar ₁ and Ar ₂ each independently represent a group represented by formula (A):

wherein Ra represents a monovalent group.

4. The dye according to item 1, wherein the dye represented by formula (1) is the dye represented by formula (3):

Wherein R ₅ , R ₆ , R ₇ and R ₈ each independently represent a monovalent group, Ar ₃ represents a divalent linking group, and M represents a hydrogen atom or a cation.

5. The dye according to item 1, wherein the dye represented by formula (1) is the dye represented by formula (4):

Wherein R ₉ and R ₁₀ each independently represent a monovalent group, Ar ₄ and Ar ₅ each independently represent an aryl group or a heterocyclic group, Ar ₆ represents a divalent linking group, and M represents a hydrogen atom or a cation.

6. The dye according to item 5, wherein Ar ₄ and Ar ₅ each independently represent a group represented by formula (A):

wherein Ra represents a monovalent group.

7. An ink comprising the dye according to any one of 1-6.

8. An inkjet recording method comprising forming an image using the ink according to item 7.

9. An ink sheet comprising the dye according to any one of 1-6.

10. A toner comprising the dye according to any one of 1-6.

11. A color filter comprising the dye according to any one of 1-6.

Advantages of the invention

The dyes of the present invention exhibit excellent storage stability in inks, have excellent absorption properties in color reproducibility as trichromatic dyes, and have sufficient resistance to light, heat, humidity and reactive gases in the environment. Also, these dyes can be used in various coloring compositions, which can provide color images or coloring materials excellent in hue and fastness, such as printing inks for inkjet printing, ink flakes in thermal recording materials, ink sheets for electrophotography, etc. Toners, color filters used in displays such as LCDs or PDPs, or image forming devices such as CCDs, and dyeing solutions for dyeing various fibers. Specifically, the use of the dye can provide an inkjet recording ink having excellent storage stability and an inkjet recording method which can form an inkjet recording ink having good color tone and high resistance to light and active gases in the environment, especially ozone An image of the properties of the gas.

Detailed description of the invention

The present invention is described in detail below.

(azo dyes)

The azo dye of the present invention is an azo dye represented by the foregoing formula (1).

Formula (1) is described below.

The monovalent groups represented by R ₁ , R ₂ and Z are the same as the substituents of the aryl group described later herein.

The dye has two azo groups in the molecule and is divided into two categories: (1) one is a dye with a group in the molecule, and the group has two azo groups as substituents; and (2) Another class is dyes with two groups, each of which has an azo group. As the former group substituted with an azo group and the latter group having an azo group, a heterocyclic group is preferable. Preferable examples of the heterocyclic ring constituting the heterocyclic group include 5-pyrazolone ring, 5-aminopyrazole ring, oxazolone ring, barbituric acid ring, pyridine ring, rhodanine ring, pyrazolidinedi Ketone ring, pyrazolopyridone ring and merdramic acid ring. Among them, a 5-pyrazolone ring and a 5-aminopyrazole ring are preferable, and a 5-aminopyrazole ring is particularly preferable.

In the present invention, M represents a hydrogen atom or a cation. Examples of cations represented by M include alkali metal ions, ammonium and quaternary ammonium cations. Among them, Li, Na, K, NH ₄ and NR ₄ are preferred, wherein R represents an alkyl or aryl group which is the same as the alkyl or aryl group described later herein.

Among the azo dyes represented by formula (1), dyes represented by formula (2), (3) or (4) are preferred.

The monovalent group represented by R ₃ and the monovalent group represented by R ₄ in formula (2) are each the same as the substituent of the aryl group described later herein. Preferable examples thereof include alkyl, cycloalkyl, aralkyl, alkoxy, aryl, amino, carboxyl (optionally forming a salt) and carbamoyl, among which alkyl (preferably containing 1 to 5 carbon atoms) is more preferred , such as methyl, ethyl, butyl or tert-butyl). The detailed description of these substituents is the same as the substituents described later herein.

A heterocyclic ring as the heterocyclic group represented by Ar ₁ or Ar ₂ is preferably a 5- or 6-membered ring, which may also be condensed with other rings. Also, these heterocycles may be aromatic heterocycles or non-aromatic heterocycles. Examples include pyridine, pyrazine, pyridazine, quinoline, isoquinoline, quinazoline, cinnoline, 2,3-naphthyridine, quinoxaline, pyrole, indole, furan, benzo Furan, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, azole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzo and isoxazole, pyrrolidine, piperidine, piperazine, tetrahydroimidazole and thiazoline. Among them, an aromatic heterocycle is preferable. Preferred illustrative examples thereof include pyridine, pyrazine, pyridazine, pyrazole, imidazole, benzimidazole, triazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole and thiadiazole. More preferable examples thereof include imidazole, benzoxazole and thiadiazole, most preferably thiadiazole (preferably 1,3,4-thiadiazole or 1,2,4-thiadiazole). They may have substituents. Examples of the substituent are the same as those of the aryl group described later herein.

The aryl group represented by Ar ₁ and the aryl group represented by Ar ₂ each include substituted and unsubstituted aryl groups. As the substituted or unsubstituted aryl group, an aryl group having 6 to 30 carbon atoms is preferred. Examples of the substituent of the aryl group include a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group (optionally forming a salt ), alkoxy, aryloxy, silyloxy, heterooxyl, acyloxy, carbamoyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amino (including anilino) , amido, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoylamino, alkylsulfonylamino, arylsulfonylamino, mercapto, alkylthio, arylthio, heterocyclic sulfur radical, sulfamoyl, sulfo (optionally forming a salt), alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, amino Formyl, imino, phosphino, phosphinyl, phosphinyloxy, phosphinylamino and silyl groups.

As the aryl group represented by Ar ₁ and the aryl group represented by Ar ₂ , a substituted phenyl group is more preferable (the substituent is preferably a carboxyl group or a sulfo group).

Substituents for aryl groups are described in more detail below.

The halogen atom is a chlorine atom, a bromine atom or an iodine atom.

Alkyl includes substituted and unsubstituted alkyl. As the substituted or unsubstituted alkyl group, an alkyl group having 1 to 30 carbon atoms is preferred. Examples of these substituents are the same as those of the aryl group. Among them, a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (optionally forming a salt), and a carboxyl group (optionally forming a salt) are preferable. Examples of the alkyl group include methyl, ethyl, butyl, tert-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl and 4-sulfobutyl.

Cycloalkyl includes substituted cycloalkyl and unsubstituted cycloalkyl. A substituted or unsubstituted cycloalkyl group preferably contains 5 to 30 carbon atoms. Examples of the substituent are the same as those of the aryl group. Examples of cycloalkyl groups include cyclohexyl, cyclopentyl and 4-n-dodecylcyclohexyl.

Aralkyl includes substituted aralkyl and unsubstituted aralkyl. As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferred. Examples of the substituent are the same as those of the aryl group. Examples of aralkyl groups include benzyl and 2-phenethyl.

Alkenyl is straight-chain, branched or cyclic, substituted or unsubstituted alkenyl. Preferable examples thereof include substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl and 2-cyclohexen-1-yl.

The alkynyl group is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and ethynyl and propargyl are exemplified.

The aryl group is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl and o-hexadecanoylaminophenyl.

The heterocyclic group is a monovalent group formed by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered aromatic heterocyclic group containing 3 to 30 carbon atoms. Examples thereof include 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl and morpholinyl.

Alkoxy includes substituted alkoxy and unsubstituted alkoxy. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Examples of the substituent are the same as those of the aryl group. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octoxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

Aryloxy is a substituted or unsubstituted aryloxy group containing 6-30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy and 2-tetradecylaminophenoxy.

The silyloxy group is a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy and tert-butyldimethylsilyloxy.

The heterocyclic oxy group is a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, such as 1-phenyltetrazol-5-oxyl and 2-tetrahydropyranyloxy.

Acyloxy is formyloxy, substituted or unsubstituted alkylcarbonyloxy containing 2-30 carbon atoms or substituted or unsubstituted arylcarbonyloxy containing 6-30 carbon atoms, for example formyl Acyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy.

Carbamoyloxy is a substituted or unsubstituted carbamoyloxy group containing 1-30 carbon atoms, such as N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyl oxy, morpholinylcarbonyloxy, N,N-di-n-octylaminocarbonyloxy and N-n-octylcarbamoyloxy.

Alkoxycarbonyloxy is a substituted or unsubstituted alkoxycarbonyloxy group containing 2-30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy and n-octylcarbonyloxy.

Aryloxycarbonyloxy is a substituted or unsubstituted aryloxycarbonyloxy group containing 7-30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy and p- n-hexadecyloxyphenoxycarbonyloxy.

The amino group is a substituted or unsubstituted alkylamino group containing 1-30 carbon atoms or a substituted or unsubstituted arylamino group containing 6-30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino and 3,5-dicarboxyanilino.

Amylamino is formylamino, substituted or unsubstituted alkylcarbonylamino containing 1-30 carbon atoms or substituted or unsubstituted arylcarbonylamino containing 6-30 carbon atoms, such as formylamino, acetyl Amino, pivaloylamino, lauroylamino, benzamido, and 3,4,5-tri-n-octyloxyphenylcarbonylamino.

Aminocarbonylamino is a substituted or unsubstituted aminocarbonylamino containing 1-30 carbon atoms, such as carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino and Morpholinylcarbonylamino.

Alkoxycarbonylamino is a substituted or unsubstituted alkoxycarbonylamino containing 2-30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecane Oxycarbonylamino and N-methyl-methoxycarbonylamino.

Aryloxycarbonylamino is substituted or unsubstituted aryloxycarbonylamino containing 7-30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino and m-n-octyloxyphenoxy ylcarbonylamino.

Sulfamoylamino is a substituted or unsubstituted sulfamoylamino group containing 0-30 carbon atoms, such as sulfamoylamino, N, N-dimethylsulfamoylamino and N-octylaminosulfonyl Amino.

Alkylsulfonylamino or arylsulfonylamino is a substituted or unsubstituted alkylsulfonylamino group containing 1-30 carbon atoms or a substituted or unsubstituted arylsulfonylamino group containing 6-30 carbon atoms, Examples include methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino and p-methylsulfonylamino.

Alkyl sulfide is a substituted or unsubstituted alkyl sulfide having 1 to 30 carbon atoms, such as methyl sulfide, ethyl sulfide and n-hexadecyl sulfide.

The arylthio group is a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio and m-methoxyphenylthio.

The heterocyclic thio group is a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio and 1-phenyltetrazol-5-ylthio.

Sulfamoyl is a substituted or unsubstituted sulfamoyl group containing 0-30 carbon atoms, such as N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl and N-(N'-phenylcarbamoyl)sulfamoyl.

Alkylsulfinyl or arylsulfinyl is a substituted or unsubstituted alkylsulfinyl group containing 1-30 carbon atoms or a substituted or unsubstituted arylsulfinyl group containing 6-30 carbon atoms, Examples are methylsulfinyl, ethylsulfinyl, phenylsulfinyl and p-methylphenylsulfinyl.

Alkylsulfonyl or arylsulfonyl is a substituted or unsubstituted alkylsulfonyl group containing 1-30 carbon atoms or a substituted or unsubstituted arylsulfonyl group containing 6-30 carbon atoms, such as methyl Sulfonyl, ethylsulfonyl, phenylsulfonyl and p-methylphenylsulfonyl.

Acyl is formyl, alkylcarbonyl containing 2-30 carbon atoms, substituted or unsubstituted arylcarbonyl containing 7-30 carbon atoms or heterocyclic carbonyl containing 4-30 carbon atoms, such as acetyl , pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl, 2-pyridylcarbonyl and 2-furylcarbonyl.

Aryloxycarbonyl is a substituted or unsubstituted aryloxycarbonyl group containing 7-30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl and p-tert Butylphenoxycarbonyl.

The alkoxycarbonyl group is a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl and n-octadecyloxycarbonyl.

Carbamoyl is a substituted or unsubstituted carbamoyl group containing 1-30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N- Di-n-octylcarbamoyl and N-(methylsulfonyl)carbamoyl.

The phosphino group is a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethyl phosphino, diphenyl phosphino and methylphenoxy phosphino.

The phosphinyl group is a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl and diethoxyphosphinyl.

The phosphinyloxy group is a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

The phosphinylamino group is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino and dimethylaminophosphinylamino.

The silyl group is a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as a trimethylsilyl group, a tert-butyldimethylsilyl group and a phenyldimethylsilyl group.

Among the substituents of the aryl group, the substituent having hydrogen may be replaced with the above substituent while the hydrogen atom is removed. Examples of such functional groups include alkylcarbonylaminosulfonyl, arylcarbonylaminosulfonyl, alkylsulfonylaminocarbonyl and arylsulfonylaminocarbonyl. Specific examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl and benzoylaminosulfonyl.

Among the dyes represented by the above formula (2), those in which Ar ₁ and Ar ₂ each independently represent a heterocyclic group are preferred, and more preferred are those in which Ar ₁ and Ar ₂ each independently represent a group of the above formula (A).

In formula (A), Ra represents a monovalent group. The monovalent group represented by Ra is the same as the monovalent group represented by R ₁ or R ₂ in formula (1), and the preferred range is also the same. More preferably, Ra represents -L-Ph or -Ph (wherein Ph represents a substituted or unsubstituted phenyl group, wherein the substituent is the same as the monovalent group represented by R ₁ or R ₂ in formula (1), and L represents a divalent linking group and is the same as Ar ₃ in formula (3)). Even more preferably, Ra represents -S-Ph or -Ph (wherein Ph represents substituted or unsubstituted phenyl).

Formula (3) will be described in detail below. The monovalent group represented by R ₅ and the monovalent group represented by R ₆ are each the same as the monovalent group of R ₃ or R ₄ . The monovalent group represented by R ₇ and the monovalent group represented by R ₈ are each the same as the above substituent for the aryl group. Furthermore, R ₇ and R ₈ each preferably represent a halogen atom, OM (wherein M represents a hydrogen atom or a cation), an alkoxy group, an alkylthio group, an arylthio group, an amino group or a heterocyclic group. These substituents are the same as previously described herein.

The divalent group represented by _Ar is preferably an alkylene group (for example, methylene, ethylene, propylene, butylene or pentylene), an alkenylene group (for example, vinylidene or propenylene), Alkynylene (for example, ethynylene or propynylene), arylene (for example, phenylene or naphthylene), divalent heterocyclic group (for example, 6-chloro-1,3,5-tri Oxazine-2,4-diyl, pyrimidine-2,4-diyl, quinoxaline-2,3-diyl or pyridazine-3,6-diyl), -O-, -CO-, -NR - (wherein R represents a hydrogen atom, an alkyl group or an aryl group), -S-, -SO ₂ -, -SO- or a combination thereof (for example, -NHCH ₂ CH ₂ NH- or -NHCONH-).

The alkylene group, alkenylene group, alkynylene group, arylene group, and divalent heterocyclic group, and the alkyl or aryl group of R may have one or more substituents. Examples of the substituent are the same as those of the aryl group. The alkyl and aryl groups for R are the same as previously defined herein.

More preferably, the divalent alkylene group is an alkylene group having 10 or fewer carbon atoms, an alkenylene group having 10 or fewer carbon atoms, an alkynylene group having 10 or fewer carbon atoms , an arylene group containing 6-10 carbon atoms, -S-, -SO-, -SO ₂ - or a combination thereof (for example, -SCH ₂ CH ₂ S- or -SCH ₂ CH ₂ CH ₂ S-) .

The total number of carbon atoms of the divalent linking group is preferably 0-50, more preferably 0-30, most preferably 0-10.

Equation (4) is described below. The monovalent group of R ₉ and the monovalent group of R ₁₀ are each the same as the monovalent group of R ₃ or R ₄ in formula (2). The aryl and heterocyclic groups represented by Ar ₄ and the aryl and heterocyclic groups represented by Ar ₅ are the same as the aryl and heterocyclic groups represented by Ar ₁ or Ar ₂ in formula (2), among which heterocyclic groups are preferred. The divalent linking group represented by Ar ₆ is the same as that of Ar ₃ in formula (3).

Among the dyes represented by formula (2), (3) or (4), the dye represented by formula (2) is preferable.

In the present invention, in the case where the compound represented by formula (1), (2), (3) or (4) is required to be hydrophilic, it is preferred that the compound has two or more, more preferably 2-10 , especially preferably 3-6 hydrophilic groups. However, the compound may not have a hydrophilic group without using water as a medium.

As the hydrophilic group, any ion-dissociating group can be used. Specific examples thereof include sulfo, carboxyl (including salts thereof), hydroxyl (optionally forming salts), phosphono (optionally forming salts) and quaternary ammonium salts, among which sulfo, carboxyl and hydroxyl (including their salts) are preferred.

Considering color reproducibility, the dye represented by formula (1), (2), (3) or (4) has an absorption maximum in H ₂ O of preferably 380-490 nm, more preferably 400-480 nm, particularly preferably 420-460 nm wavelength (λmax).

Specific examples of dyes represented by formula (1), (2), (3) or (4) (Illustrative Dyes 1-57) are shown below. However, the dyes used in the present invention are not limited to them.

The specific examples below are represented by the structure of the free acid, but they can be used in the state of their salts. Preferable examples of the counterion of the salt include alkali metals (for example, lithium, sodium and potassium), ammonium and organic cations (for example, pyridinium, tetramethylammonium and guanidinium).

The dyes of the present invention can be synthesized according to the method for the synthesis of dye 1 described later herein.

As for the use of the dye of the present invention, image recording materials for forming images, especially color images, especially inkjet recording materials, thermal recording materials, pressure-sensitive recording materials, electrophotography, etc. Recording materials, transfer type silver halide photosensitive materials, printing inks and recording pens, preferably inkjet recording materials, thermal recording materials and recording materials for electrophotography, more preferably inkjet recording materials.

Also, the dye of the present invention can be coated on color filters for recording and reproducing color images, which are used in solid imaging devices such as CCD or displays such as LCD and PDP, and dyeing solutions for dyeing various fibers.

The physical properties of the dyes of the present invention such as solubility, dispersibility and thermal mobility can be adjusted to suit the application by selecting the substituents therein. Also, the dye of the present invention may be used in a dissolved state, an emulsified emulsion state, or a solid dispersion state depending on the system used.

(ink)

The ink of the present invention refers to an ink containing at least one dye of the present invention. The ink of the present invention may contain a medium, and in the case of using a solvent as a medium, the ink is particularly preferably an inkjet recording ink. The ink of the present invention can be prepared using an oleophilic medium or an aqueous medium as a medium and dissolving and/or dispersing the dye of the present invention in the medium. Preference is given to using inks containing aqueous media. If necessary, the ink of the present invention may contain other additives within a range not impairing the effects of the present invention. Examples of other additives include known additives (described in JP-A-2003-306623) such as anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, Antifungal agents, pH regulators, surface tension regulators, defoamers, viscosity regulators, dispersants, dispersion stabilizers, rust inhibitors and chelating agents. In the case of water-soluble inks, these various additives are added directly to the ink solution. In the case of using an oil-soluble dye as a dispersion, it is usually added to the dispersion after preparation of the dye dispersion, but the oil-soluble dye may be added to the oil phase or the water phase at the time of preparation.

In the case of dispersing the dye of the present invention into an aqueous medium, it is preferable to disperse colored fine particles containing the dye and an oil-soluble polymer in JP-A-11-286637, JP-A-2001-240763 (Japanese Patent Application 2000 -78491), JP-A-2001-262039 (Japanese Patent Application No. 2000-80259) and JP-A-2001-247788 (Japanese Patent Application No. 2000-62370) described in the aqueous medium, or will be dissolved in high boiling point organic The dyestuff of the present invention in the solvent is dispersed in JP-A-2001-262018 (Japanese patent application 2000-78454), JP-A-2001-240763 (Japanese patent application 2000-78491), JP-A-2001-335734 (Japanese patent application application 2000-203856) and in the aqueous solutions described in Japanese Patent Application 2000-203857. In the case of dispersing the dye of the present invention into an aqueous medium, specific usage methods, oil-soluble polymers, high-boiling organic solvents, additives and their amounts described in the foregoing patent documents can be preferably used. In addition, the azo dye of the present invention can be dispersed as a solid in a fine particle state. At the time of dispersion, a dispersant or a surfactant can be used. As a dispersing device, a simple stirrer or a high-speed mixer, a stirring device in a pipeline, a mill (for example, a colloid mill, a ball mill, a sand mill, an attritor, a roller mill or an agitator), an ultrasonic device can be used or high-pressure emulsification equipment (high-pressure homogenizer; examples of specific commercially available equipment include GAULIN homogenizer, microfluidizer, and DeBEE2000). As the preparation method of the above-mentioned inkjet recording ink, in addition to the above-mentioned patent documents, in JP-A-5-148436, JP-A-5-295312, JP-A-7-97541, JP-A-7-82515 , JP-A-7-118584, JP-A-11-286637 and JP-A-2001-271003 (Japanese Patent Application No. 2000-87539), which can be used to prepare the present invention for inkjet recording ink.

As the aforementioned aqueous medium, a mixture containing water as a main component and, if necessary, a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent used include organic solvents described in JP-A-2003-306623. In addition, water-miscible organic solvents may be used in combination of two or more.

The dye of the present invention is contained in the ink of the present invention for inkjet recording in an amount of preferably 0.1 to 120 parts by weight, more preferably 0.2 to 10 parts by weight, and even more preferably 0.5 to 9 parts by weight relative to 100 parts by weight of the ink. Furthermore, in the ink of the present invention for inkjet recording, other dyes may be used in admixture with the dye of the present invention. In the case where two or more dyes are used in combination, the total amount of the dyes is preferably within the above range.

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

Also, the ink of the present invention for inkjet recording may contain the dye of the present invention and other dyes other than the dye of the present invention. As the yellow dye that can be used, the magenta dye that can be used, and the cyan dye that can be used, any dyes can be used, and those described in paragraphs 0090-0092 of JP-A-2003-306623 can be used. Examples of black materials that can be used include dispersions of disazo, trisazo and tetrasazo dyes and carbon black.

(Inkjet recording method)

The inkjet recording method of the present invention is on a known image receiving material, namely plain paper, resin coated paper, for example JP-A-8-169172, JP-A-8-27693, JP-A-2-276670 , JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995, JP - Special paper for inkjet recording, film, paper for inkjet recording and electrophotographic recording, cloth, glass, metal or Images are formed on ceramics by applying energy to ink for inkjet recording. Further, as the inkjet recording method of the present invention, the description in paragraph 0093-0105 of JP-A-2003-306623 can be referred to.

When forming an image, a polymer latex compound may be used together for the purpose of imparting gloss, or water repellency, or improving weather resistance. Regarding the timing of adding the latex compound to the image-receiving material, it may be added before or after adding the colorant, or may be performed at the same time as adding the colorant. Therefore, as to where the latex compound is added, the latex compound may be added to the image-receiving sheet or to the ink, or the latex compound may be used only as a liquid material of the polymer latex. In particular, JP-A-2002-166638 (Japanese Patent Application 2000-363090), JP-A-2002-121440 (Japanese Patent Application 2000-315231), JP-A-2002-154201 (Japanese Patent Application 2000 -354380), JP-A-2002-144696 (Japanese Patent Application 2000-343944), JP-A-2002-080759 (Japanese Patent Application 2000-268952), Japanese Patent Application 2000-299465 and Japanese Patent Application 2000-297365 the method described.

(toner)

The amount of the dye of the present invention per 100 parts by weight of the toner is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 1-10 parts by weight, most preferably 2-10 parts by weight.

As the binder resin for the toner to which the dye of the present invention is added, any and all commonly used binders can be used. Examples thereof include styrene-based resins, acrylic resins, styrene/acrylic resins, and polyester resins.

Inorganic fine powder or organic fine particle may additionally be added to the toner for the purpose of improving fluidity or for controlling electrostatic charge. Silica fine particles and titania fine particles whose surfaces are treated with an alkyl group-containing coupling agent are preferably used. In addition, they have a number average primary particle diameter of preferably 10 to 500 nm, and are added to the toner in an amount of 0.1 to 20% by weight.

As the release agent, any commonly used release agent can be used. Examples thereof include olefins such as low-molecular polypropylene, low-molecular polyethylene, and ethylene-propylene copolymers, and waxes such as microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. Its addition amount in the toner is preferably 1 to 5% by weight.

A charge control agent may be added as needed, and a colorless agent is preferable in view of color forming performance. Examples thereof include those of the quaternary ammonium salt structure and those of the calixarene structure.

As the carrier, any non-coated carrier consisting only of magnetic material particles such as iron or ferrite and a resin-coated carrier including magnetic material particles whose surface is coated with a resin can be used. The average particle diameter of the carrier is preferably 30 to 150 μm relative to the volume average particle.

The image forming method for coating the toner of the present invention is not particularly limited, and examples thereof include an image forming method by repeatedly forming a color image and transferring it, formation of an image formed on an electrophotographic photoreceptor by continuous transfer Method for color image, and forming color image on intermediate transfer body by continuously transferring image formed on electrophotographic photoreceptor to intermediate transfer body and transferring the color image to image forming member such as paper method of forming a color image.

(thermal recording (transfer) material)

The thermal recording material is composed of an ink sheet comprising a carrier on which the dye of the present invention and a binder are coated, and a dye that will move in accordance with thermal energy added from a thermal head in accordance with an image recording signal Fixed image receiver sheet. The ink sheet can be prepared by dissolving the compound of the present invention and a binder in a solvent or dispersing the compound as fine particles in a solvent to prepare an ink solution, applying the ink solution to a carrier, and applying the applied ink The solution dries to form. The amount of ink coated on the carrier is not particularly limited, but is preferably 30-1000 mg/m ² . As preferable binder resins, ink solvents, carriers and image-receiving sheets, those described in JP-A-7-137466 can be preferably used.

When using a thermal recording material as a thermal recording material that can record full-color images, it is preferable to continuously coat a cyan ink sheet containing a thermally diffusible cyan dye that can form a cyan image, a thermal ink sheet that can form a magenta image, etc. A magenta ink sheet with a diffusible magenta dye, and a yellow ink sheet with a thermally diffusible yellow dye that can form a yellow image to form a full color image. Likewise, an ink sheet containing a black image-forming substance can also be formed as needed.

(color filter)

As a method of forming a color filter, there are at first a method of patterning with a photoresist and then dyeing, and a method of patterning with a photoresist, such as JP-A-4-163552, JP-A-4- 128703 and JP-A-4-175753. As a method used in the case of adding the dye of the present invention to a color filter, any method can be used. As a preferred method, it can be described as a method of forming a color filter comprising the steps of exposing a positive-working composition including a thermosetting composition, a quinone diazide, a crosslinking agent, a dye, and a solvent and Apply to the substrate through a mask, develop the exposed part to form a positive resist pattern, expose the entire positive resist pattern, and then fix the exposed resist pattern, such as JP-A-4-175753 and described in JP-A-6-35182. Also, an RGB primary color base color filter or a YMC compensation color base color filter can be obtained by forming a black matrix in a conventional manner. The amount of dye used in the color filter is also not limited, but an amount of 0.1 to 50% by weight is preferred.

As the thermosetting resin for forming the color filter, quinonediazide, crosslinking agent and solvent and their amounts, those described in the aforementioned patent documents and their amounts can be preferably used.

Detailed ways

Example

The present invention is described in more detail with reference to the following examples, but the present invention should not be construed as being limited thereto.

Example 1

As a typical example, the synthesis method of Dye 1 is described below. Each step in the synthesis examples can be performed according to known synthesis methods (see JP-A-2003-277662 and the specification of Japanese Patent Application No. 2003-286844).

(synthesis example)

(1) 18.5 g of NaHCO ₃ and 185 ml of H ₂ O were heated to 40° C., and a solution of 18.4 g of compound a in 48 ml of acetone was added thereto, followed by stirring for 1 hour. After the reaction solution was concentrated to reduce the amount of acetone, 40 g of hydrazine was added thereto, and the mixture was stirred at room temperature for 3 hours. Crystals thus precipitated were collected by filtration to obtain 14 g of compound b.

(2) 10 ml of 1N NaOH was added to a mixture of 10.5 g of compound b, 20 g of compound c and 330 ml of H ₂ O, and the resulting mixture was heated for 3 hours. The reaction mixture was filtered, and the filtrate was acidified with acetic acid. Crystals thus precipitated were collected by filtration to obtain 4 g of compound d.

(3) 15 g of compound e was diazotized and added to a mixture of 3 g of compound d, 100 ml of CH ₃ OH and 16 g of CH ₃ COOK at 5°C. Crystals thus precipitated were collected by filtration, and subjected to column chromatography to obtain 4.9 g of Dye 1 .

λmax 451.7 nm (H ₂ O), ε: 5.88×10 ⁴ (dm ³ ·cm/mol).

Other dyes can be synthesized in the same manner.

Example 2

Synthesis examples of the synthetic dye 20 are described below. Dye 20 can be similarly synthesized by carrying out the synthesis method of Dye 1. The λmax of the synthesized dye in H ₂ O is shown in Table 1.

Table 1

Example 3

Pure water (resistance value: 18 MΩ or more) was added to the following components to make 1 liter, and the resulting mixture was stirred under heating for 1 hour. Thereafter, the mixture was filtered through a 0.25 μm microfilter under reduced pressure to prepare a yellow ink solution Y-101.

(Formulation of yellow ink Y-101)

(solid component)

Dye of the invention 1 40 g/l

Proxel (produced by Zeneca) 1.5g/l

Urea 20g/l

(liquid component)

Triethylene glycol monobutyl ether (DGB) 100g/l

Glycerin (GR) 115g/l

Triethylene glycol (TEG) 100g/l

2-Pyrrolidone 35g/l

Triethanolamine (TEA) 8g/l

Surfynol STG(SW) 10g/l

Ink solution Y-102 was prepared in the same manner as that of ink solution Y-101 except that the dye was changed as shown in Table 2 below.

In this case, ink solutions 101 and 102 were prepared using comparative dyes a and b shown in Table 2 as comparative ink solutions.

When changing the dye, the added amount of the dye is adjusted to be equimolar to the dye in the ink solution Y-101.

The inks for inkjet recording prepared in Examples (ink solutions Y101 and Y102) and comparative examples (ink solutions 101 and 102) were subjected to the following evaluations. The results are shown in Table 2.

In addition, in Table 2, evaluation was performed by adding each ink for inkjet recording to a cartridge for yellow ink of an inkjet printer PM920C manufactured by EPSON and printing a monochrome image pattern and a gray image pattern in which the image density gradually changed "Hue", "Lightfastness", "Ozone (gas) resistance" and "Heat resistance". Images were printed on image-receiving sheets, "Kotaku" (photographic paper suitable for EPSON inkjet printers), and evaluated for image quality and image fastness.

(evaluation test)

<hue>

Images were visually evaluated in three grades of A (best), B (good), and C (poor). The λmax values on photographic paper "Kotaku" are also shown.

<Lightfastness>

The image density Ci immediately after printing was measured by a reflection densitometer (X-rite 310TR). Then, the image was irradiated with a xenon lamp (85,000 lux) for 7 days using a weather meter manufactured by Atlas, and the image density Cf was measured to determine the dye retention ratio Cf/Cix100 for evaluation. The dye retention ratio was evaluated at three points with reflection densities of 1, 1.5 and 2, respectively. A sample showing a dye retention ratio of 70% or more at three densities was rated as A, a sample showing a dye retention ratio of less than 70% at two of the three densities was rated as B, and all three densities were rated as B. The sample below showing a dye retention ratio of less than 70% was evaluated as C.

<Ozone (gas) resistance>

The imaged photographic paper was left standing for 10 days in a box whose ozone gas density was adjusted to 5 ppm, and the image density of the paper before and after being left standing under an ozone gas environment was measured using a reflection densitometer (X-rite 310TR), thereby Determine the dye retention ratio. In addition, reflection densities were measured at three points with densities of 1, 1.5, and 2, respectively. The ozone gas density in the cartridge was detected by an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.

There are three grades for evaluation. That is, a sample showing a dye retention ratio of 80% or more at all three densities was rated as A, a sample showing a dye retention ratio of less than 80% at one or two of the three densities was rated as B, and Samples showing less than 70% dye retention at all three densities were rated C.

<Heat resistance>

The image density of the samples before and after storage at 80° C. and 70% RH for 10 days was measured using a reflection densitometer (X-rite 310TR) for evaluation. The dye retention ratio was determined at three points with reflection densities of 1, 1.5 and 2, respectively. A sample showing dye retention of 90% or greater at all three densities was rated as A, a sample showing dye retention of less than 90% at two of the three densities was rated as B, and all three densities were rated as B. A sample showing a dye retention ratio of less than 90% in density was rated as C.

<Ink Stability>

The ink solution obtained above was stored at 70° C. for 6 days, and the dye retention ratio was measured by liquid chromatography for evaluation. An ink solution showing a dye retention ratio of 95% or more was rated as A, an ink solution showing a dye retention ratio of 85% to less than 95% was rated as B, and an ink solution showing a dye retention ratio of less than 85% was rated for C.

The table below shows the results thus obtained.

Table 2

samples Dye Hue (λmax) Lightfastness Ozone resistance Persistence Ink stability Remark Y101 1 A(455nm) A A A A this invention Y102 4 A(453nm) A A A A this invention 101 a A(446nm) A A A B comparative example 102 b A(448nm) A A A C comparative example

From the results shown in the table above it is clear that all factors were excellent in all systems using the inks of the present invention. In particular, they have excellent ink stability compared to the systems of the comparative examples.

contrast dye a

contrast dye b

Example 4

Using the same ink and the same printer as those used in Example 3, the image was printed on inkjet paper of photographic glossy paper "Gasai" manufactured by FujiPhoto Film Co., Ltd., and then the same evaluation as in Example 3 was performed, The same results as in Example 3 were obtained.

Example 5

(Preparation of ink solution D)

At 70°C, 62.5g of the dyestuff of the present invention and 7.04g of sodium dioctylsulfosuccinate were dissolved in 4.22g of the following high-boiling organic solvent (s-2), 5.63g of the following high-boiling organic solvent (s-11 ) and 50ml of ethyl acetate in a mixture. To this mixture solution was added deionized water under stirring with a magnetic stirrer to obtain an oil-in-water type crude dispersion. Next, the resulting crude mixture was passed through a microfluidizer (MICROFLUIDEX INC) 5 times at a pressure of 600 bar to reduce the size of the oil droplets. Also, the resulting emulsion was subjected to a solvent removal step in a rotary evaporator until no ethyl acetate odor could be detected. Ink solution D was prepared by adding 140 g of diethylene glycol, 50 g of glycerin, 7 g of SURFYNOL 465 (Air Products & Chemicals) and 900 ml of deionized water to the thus obtained miniemulsion of the hydrophobic dye. The ink had a pH of 8.5, a viscosity of 4.1 mPa·S and a surface tension of 33 mN/m.

(Preparation of ink solution 103)

Ink solution 103 was prepared in the same manner as ink solution D, except that the inventive dye used in ink solution D was changed to an equimolar amount of the comparative dye shown in Table 3. This ink solution has the same pH, the same viscosity, and the same surface tension as ink solution D.

(image recording and evaluation)

Ink Solution D and Comparative Ink Solution 103 were evaluated as follows. The results are shown in Table 3 below.

In addition, in Table 3, "color tone (λmax)", "light resistance", "ozone (gas) resistance", "heat resistance" and "ink stability" have the same values as those described in Example 3, respectively. meaning.

table 3

samples Dye Hue (λmax) Lightfastness Ozone resistance heat resistance Ink stability D 6 A(450nm) A A A A 103 Contrast Dye C4 B(430nm) C C A A

contrast dye C

As is clear from Table 3, the ink of the present invention for inkjet recording has excellent color tone, light fastness, ozone fastness, heat resistance and ink stability.

Example 6

Using the same ink and the same printer as used in Example 5 to print an image on an inkjet paper of a photographic glossy paper "Gasai" manufactured by Fuji PhotoFilm Co., Ltd., and then perform the same evaluation as in Example 5, the obtained Example 5 had the same result.

Example 7

3 parts by weight of the dye 5 of the present invention and 100 parts by weight of a resin for toner (styrene-acrylate copolymer; trade name Himer TB-1000F (manufactured by Sanyo Chemical Industries, Ltd.)) were mixed and mixed in a ball mill Pulverized, then melt-kneaded by heating to 150° C., after cooling the mixture, pulverized by a hammer mill, and then finely pulverized in a pulverizer based on an air injection system. Further, the resulting fine particles are sorted to select particles having a particle diameter of 1 to 20 µm, and toner is prepared from the selected particles. 10 parts of this toner was uniformly mixed with 900 parts of carrier iron powder (trade name: EFV250/400; manufactured by Nihon Teppun) to prepare a developer. Also, samples were prepared in the same manner except that 3 parts by weight of the colorants shown in Table 4 were used. Plain paper was copied using these developers in a dry process electrophotographic copier (trade name NP-5000; manufactured by Canon Co., Ltd.).

Evaluation tests were conducted on reflective images (images on paper) and transparent images (OHP images) formed on paper and OHP, respectively, by developers containing the toner of the present invention according to the above-mentioned image forming methods in the following manner. In addition, the evaluation was performed based on the amount of deposited toner within the range of 0.7±0.05 (mg/cm ² ).

The color tone and light fastness of the images thus obtained were evaluated. The color tone was visually evaluated in three grades of best, good and poor. The evaluation results are shown in Table 4 below. In Table 4, "A" means that the color tone of the sample is the best, "B" means that the color tone of the sample is good, and "C" means that the color tone of the sample is poor.

As for the light fastness, the image density Ci immediately after recording was measured, and then the image was irradiated with a xenon lamp (85,000 lux) for 5 days using a weathering tester (Atlas C.165). Then, the image density Cf was measured to determine the dye retention ratio {(Ci-Cf)/Ci} x 100%, which was used for evaluation based on the difference in image density before and after xenon lamp irradiation. Image density was determined using a reflection densitometer (X-Rite 310TR). The results thus obtained are shown in Table 4 below. In Table 4, samples showing a dye retention ratio of 90% or more were rated as A, samples showing a dye retention ratio of 90 to 80% were rated as B, and samples showing a dye retention ratio of less than 80% were rated as c.

The transparency property of the OHP image was evaluated according to the method described below. The visible spectrum transmittance of the image was measured by "Model 330 Automatic Recording Spectrophotometer" manufactured by Hitachi, Ltd., wherein the OHP sheet without toner was used as a reference, thereby determining the spectral transmittance at 650 nm. This spectral transmittance was used as a measure of the transparency properties of the OHP image. Samples showing spectral transparency greater than 80% were rated as A, samples showing spectral transparency of 70-80% were rated as B, and samples showing spectral transmittance of less than 70% were rated as C. The results thus obtained are shown in Table 4.

Table 4

Dye Hue Lightfastness Transparency this invention 5 A A A comparative example C.I. Solvent Yellow 162 B B B

As is clear from Table 4, the toner of the present invention achieves color reproducibility with high fidelity and provides high OHP quality, so it is suitable for use as a full-color toner. Also, the toner has good light fastness, so that it can provide images that can be stored for a long time.

Example 8

(Preparation of materials that provide thermal transfer dyes)

A material (5-1) providing a thermal transfer dye was prepared using a 6-μm-thick polyethylene terephthalate film (manufactured by Teijin) whose reverse side had been treated to impart heat resistance and lubrication as a support , and the surface of the film was coated with the coating composition of the following formulation in a dry thickness of 1.5 μm according to the wire-wound coating method for providing a layer of thermal transfer dye.

Coating composition for providing a layer of thermal transfer dye

Dye 510mmol

Polyvinyl butyral resin (manufactured by Denki Kagaku 3 g

Denka Butyral 5000-A)

Toluene 40ml

Methyl ethyl ketone 40ml

Polyisocyanate (Takenate manufactured by Takeda Yakuhin 0.2ml

D110N)

Then, a material (5-2) providing a thermal transfer dye for comparison was prepared in the same manner as above except that Dye 5 was changed to the comparative dye described in Table 5.

(Preparation of thermal transfer image-receiving material)

A thermal transfer image-receiving material was prepared using a 150-μm-thick synthetic paper (YUPO-FPG-150 manufactured by Qji Yuka) as a support and coating the following composition at a dry thickness of 8 μm by a wire-wound coating method. Drying in a 100° C. oven for 30 minutes after temporary drying by a drier.

Coating composition for image receiving layer

Polyester resin (VYLON-280 manufactured by Toyobo) 22 g

Polyisocyanate (made by Dainippon Ink & Chemicals, Inc. 4 g

Made KP-90)

Amino-modified silicone oil (manufactured by Shin-etsu Silicone 0.5 g

KF-857)

Methyl ethyl ketone 85ml

Toluene 85ml

Cyclohexanone 15ml

With the thermal dye-providing layer facing the image-receiving layer, the thermal transfer dye-providing materials (5-1) and (5-2) thus obtained were superimposed on the thermal transfer image-receiving material, and used The thermal head on the carrier side of the dye-printed material was printed under the conditions of a thermal head output of 0.25 W/dot, a pulse width of 0.15-15 msec, and a dot density of 6 dots/mm, thereby printing on the image-receiving material A yellow dye was deposited in a pattern on the image receiving layer. The maximum coloring densities of the images thus obtained are shown in Table 5. The thermal transfer dye-providing material (5-1) of the present invention forms a clear image without transfer unevenness. Next, each recorded thermal transfer image-receiving material thus obtained was irradiated with an Xe lamp (17,000 lux) for 5 days, thereby measuring the light fastness of the color image. The A-state mode reflection density of the portion showing the A-state reflection density of 1.0 was measured after irradiation, and the light resistance was evaluated based on the residual value ratio (percentage) of the reflection density based on the reflection density before irradiation being 1.0. The results are shown in Table 5.

table 5

Sublimation dye available for maximum lightfastness Remarks

Dye Material Density

5-1 5 1.8 90 The present invention

5-2 Contrast dye d 1.8 52 Contrast ratio

contrast dye d

As stated earlier herein, the dyes of the invention are superior compared to the comparative dyes. Also, the color tone of the image formed by the dye of the present invention is clear.

Example 9

When preparing a color filter, spin-coat a positive-type resist composition containing a thermosetting resin, quinonediazide, a crosslinking agent, a dye, and a solvent onto a silicon wafer, and after evaporating the solvent by heating, pass through a mask. The film exposes the coating to decompose quinonediazide. After heating as necessary, the exposed coating is developed to obtain a mosaic pattern. Exposure was performed by an i-ray exposure stepper HITACHI LD-5010-I (NA=0.40) manufactured by Hitachi, Ltd. Also, as a developing solution, SOPD or SOPD-B manufactured by Sumitomo Kagaku Kogyo was used.

<Preparation of Positive Resist Composition>

The cresol novolac resin (based on polystyrene, weight-average molecular weight is 4300) obtained by the mixture (reaction molar ratio=5/5/7.5) of 3.4 weight parts by m-cresol/p-cresol/formaldehyde , 1.8 parts by weight of o-naphthoquinonediazide-5-sulfonate (average 2 hydroxyl groups are esterified) prepared from a phenol compound represented by the following formula, 0.8 parts by weight of hexamethoxymethylolmelamine, 20 parts by weight of ethyl lactate and 1 part by weight of the dyes of the present invention shown in Table 1 were mixed to obtain a positive resist composition.

Phenol compounds

<Preparation of color filter>

The positive resist composition thus obtained was applied to a silicon wafer by spin coating, after which the solvent was evaporated off. After exposing the silicon wafer to light, it was heated at 100° C., followed by alkali development to remove the exposed area, thereby obtaining a positively colored pattern with a resolution of 0.8 μm. After the entire pattern was exposed, the silicon wafer was heated at 150° C. for 15 minutes to obtain a color filter having a color complementary to yellow.

<Comparative example>

A positive resist composition was obtained by using 1 part by weight of OleozolYellow 2G manufactured by Sumitomo Kagaku Kogyo instead of the yellow dye of the present invention used in the above Examples. The positive resist composition thus obtained was applied to a silicon wafer by spin coating, and then the solvent was evaporated off. After the silicon wafer was exposed, alkali development was performed to obtain a positively colored pattern with a resolution of 1 μm. After exposing the entire pattern, the silicon wafer was heated at 150° C. for 10 minutes to obtain a yellow color filter.

<Evaluation>

The obtained transparency spectrum of each yellow color filter was measured, and the sharpness of the spectrum on the shorter wavelength side and the longer wavelength side was relatively evaluated, which is important for color reproducibility. "A" represents a good level, "B" represents an acceptable level, and "C" represents an unacceptable level. Also, each sample was irradiated with a xenon lamp (85,000 lux) for 7 days using a weathering tester (Atlas C.I65), and the image density before and after irradiation with the xenon lamp was measured, and the light fastness was evaluated based on the dye retention ratio.

Table 6

Dye absorption properties Lightfastness this invention 5 A 96% comparative example Oleozol Yellow 2G B 59%

It can be seen that the dye of the present invention exhibits a sharper spectrum on the shorter wavelength side and longer wavelength side than the dye of the comparative example, and thus is excellent in color reproducibility. Also, it is seen that the dyes of the invention are superior in light fastness compared to the comparative compounds.

Industrial Applicability

The dye of the present invention can be used in various coloring compositions capable of providing color images or coloring materials excellent in tone and fastness, such as printing inks for inkjet printing, ink flakes in thermal recording materials, toners for electrophotography, Color filters for displays such as LCD or PDP or for imaging devices such as CCD, and dyeing solutions for dyeing various fibers.

The present invention has been explained in detail and with reference to the specific embodiments, but it will be apparent to those skilled in the art that various modifications and changes can be made within the scope and spirit of the present invention.

The entire contents of each foreign patent application and each of the respective foreign patent applications from which this application claims foreign priority are incorporated herein by reference as if fully described herein.

Claims (8)

1. A dye represented by formula (2), (3) or (4):

in: R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a monovalent group selected from the group described below; each of Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ Independently represent an aryl group containing 6-30 carbon atoms or a 5-membered or 6-membered heterocyclic group, the aryl group is optionally substituted by the monovalent group, and the heterocyclic group is optionally fused with other rings combined; Ar ₃ and Ar ₆ each independently represent a divalent linking group containing 0-50 carbon atoms, and M represents a hydrogen atom or a cation; The monovalent group is selected from the following group, and is optionally further substituted with a monovalent group selected from the following group: Halogen atoms, An alkyl group containing 1-30 carbon atoms, Cycloalkyl groups containing 5-30 carbon atoms, Aralkyl groups containing 7-30 carbon atoms, Alkenyl containing 2-30 carbon atoms, Alkynyl containing 2-30 carbon atoms, Aryl groups containing 6-30 carbon atoms, A heterocyclic group containing 3-30 carbon atoms, cyano, hydroxyl, nitro, carboxyl, Alkoxy groups containing 1-30 carbon atoms, Aryloxy groups containing 6-30 carbon atoms, A siloxy group containing 3-20 carbon atoms, Heteroepoxy group containing 2-30 carbon atoms, Formyloxy, Alkylcarbonyloxy containing 2-30 carbon atoms, Arylcarbonyloxy containing 6-30 carbon atoms, Carbamoyloxy groups containing 1-30 carbon atoms, Alkoxycarbonyloxy containing 2-30 carbon atoms, Aryloxycarbonyloxy containing 7-30 carbon atoms, Alkylamino containing 1-30 carbon atoms, Arylamino containing 6-30 carbon atoms, Formamide, Alkylcarbonylamino containing 1-30 carbon atoms, Arylcarbonylamino containing 6-30 carbon atoms, Aminocarbonylamino containing 1-30 carbon atoms, Alkoxycarbonylamino containing 2-30 carbon atoms, Aryloxycarbonylamino containing 7-30 carbon atoms, Sulfamoylamino containing 0-30 carbon atoms, Alkylsulfonylamino containing 1-30 carbon atoms, Arylsulfonylamino containing 6-30 carbon atoms, Mercapto, Alkylsulfides containing 1-30 carbon atoms, An arylthio group containing 6-30 carbon atoms, A heterocyclic thio group containing 2-30 carbon atoms, A sulfamoyl group containing 0-30 carbon atoms, sulfo group, Alkylsulfinyl containing 1-30 carbon atoms, Arylsulfinyl containing 6-30 carbon atoms, Alkylsulfonyl containing 1-30 carbon atoms, Arylsulfonyl containing 6-30 carbon atoms, formyl, Alkylcarbonyl containing 2-30 carbon atoms, Arylcarbonyl containing 7-30 carbon atoms, A heterocyclic carbonyl group containing 4-30 carbon atoms, Aryloxycarbonyl containing 7-30 carbon atoms, Alkoxycarbonyl containing 2-30 carbon atoms, Carbamoyl groups containing 1-30 carbon atoms, imino, A phosphino group containing 2-30 carbon atoms, A phosphinyl group containing 2-30 carbon atoms, Phinyloxy containing 2-30 carbon atoms, A phosphinylamino group containing 2-30 carbon atoms, A silyl group having 3 to 30 carbon atoms. 2. The dye as claimed in claim 1, wherein Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ each independently represent a group represented by formula (A):

Wherein Ra represents a monovalent group selected from the following group; and is optionally also substituted with a monovalent group selected from the following group: Halogen atoms, An alkyl group containing 1-30 carbon atoms, Cycloalkyl groups containing 5-30 carbon atoms, Aralkyl groups containing 7-30 carbon atoms, Alkenyl containing 2-30 carbon atoms, Alkynyl containing 2-30 carbon atoms, Aryl groups containing 6-30 carbon atoms, A heterocyclic group containing 3-30 carbon atoms, cyano, hydroxyl, nitro, carboxyl, Alkoxy groups containing 1-30 carbon atoms, Aryloxy groups containing 6-30 carbon atoms, A siloxy group containing 3-20 carbon atoms, Heteroepoxy group containing 2-30 carbon atoms, Formyloxy, Alkylcarbonyloxy containing 2-30 carbon atoms, Arylcarbonyloxy containing 6-30 carbon atoms, Carbamoyloxy groups containing 1-30 carbon atoms, Alkoxycarbonyloxy containing 2-30 carbon atoms, Aryloxycarbonyloxy containing 7-30 carbon atoms, Alkylamino containing 1-30 carbon atoms, Arylamino containing 6-30 carbon atoms, Formamide, Alkylcarbonylamino containing 1-30 carbon atoms, Arylcarbonylamino containing 6-30 carbon atoms, Aminocarbonylamino containing 1-30 carbon atoms, Alkoxycarbonylamino containing 2-30 carbon atoms, Aryloxycarbonylamino containing 7-30 carbon atoms, Sulfamoylamino containing 0-30 carbon atoms, Alkylsulfonylamino containing 1-30 carbon atoms, Arylsulfonylamino containing 6-30 carbon atoms, Mercapto, Alkylsulfides containing 1-30 carbon atoms, An arylthio group containing 6-30 carbon atoms, A heterocyclic thio group containing 2-30 carbon atoms, A sulfamoyl group containing 0-30 carbon atoms, sulfo group, Alkylsulfinyl containing 1-30 carbon atoms, Arylsulfinyl containing 6-30 carbon atoms, Alkylsulfonyl containing 1-30 carbon atoms, Arylsulfonyl containing 6-30 carbon atoms, formyl, Alkylcarbonyl containing 2-30 carbon atoms, Arylcarbonyl containing 7-30 carbon atoms, A heterocyclic carbonyl group containing 4-30 carbon atoms, Aryloxycarbonyl containing 7-30 carbon atoms, Alkoxycarbonyl containing 2-30 carbon atoms, Carbamoyl groups containing 1-30 carbon atoms, imino, A phosphino group containing 2-30 carbon atoms, A phosphinyl group containing 2-30 carbon atoms, Phinyloxy containing 2-30 carbon atoms, A phosphinylamino group containing 2-30 carbon atoms, A silyl group having 3 to 30 carbon atoms. 3. The dye of claim 1, wherein said divalent linking group is selected from the group consisting of: Alkylene having 10 or fewer carbon atoms, alkenylene having 10 or fewer carbon atoms, alkynylene having 10 or fewer carbon atoms, arylene having 6 to 10 carbon atoms , -O-, -CO-, -NR-, -S-, -SO-, -SO ₂ - or a combination of these groups; wherein R represents a hydrogen atom, an alkyl group containing 1-30 carbon atoms or containing An aryl group of 6-30 carbon atoms. 4. An ink comprising a dye according to any one of claims 1-3. 5. An inkjet recording method comprising forming an image using the ink according to claim 4. 6. An ink sheet comprising a dye according to any one of claims 1-3. 7. A toner comprising the dye according to any one of claims 1-3. 8. A color filter comprising the dye according to any one of claims 1-3.