JP4073453B2 - Dye, ink, inkjet ink, inkjet recording method, ink sheet, color toner, and color filter - Google Patents

Description

  The present invention relates to an ink, an ink jet ink, an ink jet recording method, a method for improving weather resistance of a formed colored image material, an ink sheet, a color toner, and a color filter.

  In recent years, a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens and the like are actively used. Further, a color filter is used for recording and reproducing a color image in an imaging device such as a CCD in a photographing apparatus and in an LCD or PDP in a display. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixing method and subtractive color mixing method are used 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 dye has good yellow hue, has good yellow hue, is robust against light, wet heat and active gases in the environment, and has excellent storage stability. Is strongly desired.

  A typical example of the yellow dye skeleton used in ink jet recording inks is azo. As typical azo dyes, Japanese Patent Application Laid-Open No. 2003-277661 describes a dye having a robust triazinylpyrazole skeleton, but a dye excellent in storage stability in ink is desired.

JP 2003-277661 A

An object of the present invention is to solve the conventional problems and achieve the following objects.
That is, the present invention is 1) an absorption characteristic with excellent color reproducibility as a pigment of the three primary colors, and sufficient fastness to light, heat, humidity and the active gas in the environment, and in the ink 2) providing dyes with excellent storage stability, 2) providing colored images and coloring materials with excellent hue and fastness, inks for printing such as inkjet, ink sheets in thermal recording materials, and color toners for electrophotography Provides various colored compositions (inks) such as color filters used in displays such as LCDs, LCDs, PDPs, and CCDs, and 3) especially excellent storage stability in ink and good hue Another object of the present invention is to provide an ink for ink jet recording and an ink jet recording method capable of forming an image having high fastness against light, wet heat and active gas in the environment, particularly ozone gas.

  The present inventors have studied in detail a pyrazolylazo dye derivative aiming at a dye excellent in ink stability, having a good hue, and having high fastness to light, ozone and wet heat. The following general formula (I ) And the compounds represented by (1) to (6) have found that the above problems can be solved, and have completed the present invention. Means for solving the above problems are as follows.

<1> A dye represented by the following general formula (I).
Formula (I)

In the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group. When n is 2, R, X, Y, Z, Q, and G each represent a monovalent or divalent substituent, and at least one represents a divalent substituent. When n is 3, R, X, Y, Z, Q, G represents a monovalent, divalent, or trivalent substituent, at least two represent a divalent substituent, or at least one is trivalent. Represents a substituent of However, X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.2 or more.
<2> The dye according to claim 1, wherein at least one of substituents on the heterocyclic group represented by G is -OM (M represents a hydrogen atom or a cation).

< 3 > A dye represented by the following general formula (1), general formula (2), general formula (3), general formula (4), or general formula (5).
General formula (1)

In the formula, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, and G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle M represents a hydrogen atom or a cation. m ₁ represents an integer of 0 to 3. However, X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.2 or more.
General formula (2)

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₁ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₂₁ and m ₂₂ each independently represent an integer of 0 to 3. However, X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.2 or more.
General formula (3)

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group, L ₂ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3. However, X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.2 or more.
General formula (4)

In the formula, R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₃ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3. However, X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.2 or more.
General formula (5)

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, and L ₄ is a divalent having a Hammett's σp value of 0.2 or more. Wherein G ₁ and G ₂ each independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3.

<4> The dye according to <1> or <2>, wherein X, X ₁ and X ₂ each independently represent an electron-withdrawing group having a Hammett's σp value of 0.20 or more.
<5> X, X ₁ and X ₂ are each independently an acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, Diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group, halogen The dye according to <1> or <2>, which represents a halogenated aryloxy group, a halogenated alkylamino group, or a halogenated alkylthio group.
<6> formula (I), the general formula (1), the general formula (2), the general formula (3), the general formula (4), in the general formula (5), G, consists of _{G 1} and _{G 2} The dye according to any one of <2> to <5>, wherein the nitrogen-containing heterocycle is an S-triazine ring , a pyrimidine ring, a pyridazine ring, a pyrazine ring, or a pyridine ring .
<7> The dye according to <6>, wherein the substituent on the nitrogen-containing heterocycle described in <6> has one —OM (M represents a hydrogen atom or a cation).

< 8 > The dye according to any one of <2> to <7>, wherein the dye represented by the general formula (1) is a dye represented by the following general formula (6).
General formula (6)

_{Wherein, R 1, R 2, Y} 1, and _{Y 2} represents a monovalent _{group, X 1,} X ₂ represents a σp value of 0.20 or more electron-withdrawing group with a Hammett's substituent constant independently. Z ₁ and Z ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted An aryl group, a substituted or unsubstituted heterocyclic group is shown. M represents a hydrogen atom or a cation.

< 9 > An ink containing at least one pigment according to any one of <1> to < 8 >.

< 10 > An ink for ink jet recording using the ink described in < 9 > above.

< 11 > An ink jet recording method for forming an image using the ink according to < 10 >.

< 12 > An ink jet recording method, wherein an image is formed on an image receiving material having an ink image receiving layer containing white inorganic pigment particles on a support, using the ink according to the above < 10 >.

< 13 > A method for improving weatherability of a colored image material formed using the ink according to < 10 >.

< 14 > An ink sheet containing at least one pigment according to any one of <1> to < 8 >.

< 15 > A color toner containing at least one dye according to any one of <1> to < 8 >.

< 16 > A color filter comprising at least one pigment according to any one of <1> to < 8 >.

< 17 >
A compound represented by the following general formula (7), a salt or a hydrate thereof.
General formula (7)

(In the formula, R ₃ and R ₄ each independently represent a monovalent group, P ₁ and P ₂ each independently represent a hydrogen atom or a leaving group, and M represents a hydrogen atom or a cation.)

The coloring matter of the present invention is excellent in storage stability in ink, has absorption characteristics with excellent color reproducibility as a coloring matter of three primary colors, and is fast enough to light, heat, humidity and active gases in the environment. Have In addition, this pigment gives colored images and coloring materials excellent in 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, the ink for ink-jet recording is excellent in storage stability of the ink by using the coloring matter, has a good hue, and can form an image having high fastness against light and the active gas in the environment, particularly ozone gas. And an ink jet recording method.

Hereinafter, the present invention will be described in detail.
[Azo dye]
Here, Hammett's substituent constant σp value used in the present specification will be described briefly.
Hammett's rule is a method for determining the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to a substituent having a known value that can be found in the above-mentioned book. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule. Although the compounds represented by the general formulas (I) and (1) to (6) of the present invention are not benzene derivatives, the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense.

  The azo dye in the present invention is an azo dye represented by the general formulas (I) and (1) to (6).

  Hereinafter, the general formula (I) will be described in detail.

  In the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3.

  When n is 1, R, X, Y, Z, Q, and G represent a monovalent group, and represent a monoazo dye shown in parentheses.

  When n is 2, R, X, Y, Z, Q, and G represent a monovalent or divalent substituent. However, at least one represents a divalent substituent, and represents a bis-type azo dye of the dye shown in parentheses.

  When n is 3, R, X, Y, Z, Q, and G represent a monovalent, divalent, or trivalent substituent. However, at least two represent a divalent substituent, or at least one represents a trivalent substituent, and represents a tris-type azo dye of a dye shown in parentheses.

  Hereinafter, the general formula (I) will be described in more detail.

  In the general formula (I), preferred examples of the substituent for G are preferably 5- to 8-membered heterocyclic groups, and more preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic groups. , They may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

Examples of the heterocyclic group represented by G include pyridine, pyrazine, pyridazine, pyrimidine, 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, imidazo Examples include lysine, thiazoline, sulfolane and the like.

  When the heterocyclic group is a group that can further have a substituent, the heterocyclic group may further have the following substituents.

  C1-C12 linear or branched alkyl group, C7-C18 linear or branched aralkyl group, C2-C12 linear or branched alkenyl group, C2-C12 linear Or a branched alkynyl group, a linear or branched cycloalkyl group having 3 to 12 carbon atoms, a linear or branched cycloalkenyl group having 3 to 12 carbon atoms (the above groups having a branched chain are dissolved in a dye) Preferred are those having an asymmetric carbon, for example, methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (for example, chlorine atom, bromine atom), aryl group (for example, phenyl, 4-t-butyl) Phenyl, 2,4-di-t-amylphenyl), heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro Group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy, acylamino group (eg, acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), alkylamino group (For example, Mechi Amino, butylamino, diethylamino, methylbutylamino), arylamino groups (eg, phenylamino, 2-chloroanilino), ureido groups (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino groups (For example, N, N-dipropylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2 -Carboxyphenylthio), alkyloxycarbonylamino groups (eg methoxycarbonylamino), alkylsulfonylamino groups and arylsulfonylamino groups (eg methylsulfonylamino, phenylsulfonylamino, p-toluene) Sulfonylamino), carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl) ), A sulfonyl group (for example, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl), an alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), a heterocyclic oxy group (for example, 1-phenyltetrazole-5) -Oxy, 2-tetrahydropyranyloxy), azo groups (eg, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy groups (eg, Acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide Group (for example, N-succinimide, N-phthalimide), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio) ), Sulfinyl group (eg 3-phenoxypropylsulfinyl), phosphonyl group (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (eg phenoxycarbonyl), acyl (E.g., acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (e.g., carboxyl group, a sulfo group, a phosphono group and a quaternary ammonium group).

In the general formula (I), examples of preferred substituents of Q, R, Y and Z will be described in detail.

When Q, R, Y and Z represent a monovalent group, the monovalent group represents a hydrogen atom or a monovalent substituent. The monovalent substituent will be described in more detail. Examples of the monovalent substituent 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, an alkoxy group, and an aryl group. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonyl Amino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, A silyl group, an azo group, or an imide group can be mentioned, and each may further have a substituent.

  Among them, particularly preferred are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group. An arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic group, and a hydrogen atom, an alkyl group Most preferred are groups, aryl groups, cyano groups, or alkylsulfonyl groups.

Hereinafter, Q, R, Y, and Z will be described in more detail.

The halogen atom represented by Q, R, Y and Z represents a chlorine atom, a bromine atom or an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

The alkyl group represented by Q, R, Y and Z 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 those exemplified when G is a group capable of further having a substituent. Of these, a hydroxy group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in a salt form) or a carboxyl group (may be in a salt form) is 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 represented by Q, R, Y and Z includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the cycloalkyl group may include cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl.

The aralkyl group represented by Q, R, Y and Z includes a substituted or unsubstituted aralkyl group. 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 those exemplified when G is a group capable of further having a substituent. Examples of the aralkyl include benzyl and 2-phenethyl.

The alkenyl group represented by Q, R, Y and Z represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. Preferred examples 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.

The alkynyl group represented by Q, R, Y and Z is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.

The aryl group represented by Q, R, Y and Z is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, or o-hexadecanoylaminophenyl. It is. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent.

The heterocyclic group represented by Q, R, Y and Z is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. Yes, they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the heterocyclic group include, but are not limited to, a substitution position. Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. Can be mentioned.

The alkoxy group represented by Q, R, Y and Z includes a substituted or unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group represented by Q, R, Y and Z is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

The silyloxy group represented by Q, R, Y and Z is preferably a silyloxy group having 3 to 20 carbon atoms, and examples thereof include trimethylsilyloxy and t-butyldimethylsilyloxy.

The heterocyclic oxy group represented by Q, R, Y and Z is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

The acyloxy groups represented by Q, R, Y and Z are a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. And examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

The carbamoyloxy group represented by Q, R, Y and Z is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed.
Examples of the carbamoyloxy group include, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyl. Examples include oxy.

The alkoxycarbonyloxy group represented by Q, R, Y and Z is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

The aryloxycarbonyloxy group represented by Q, R, Y and Z is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. And the same substituents as those exemplified when is a group capable of further having a substituent. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

The amino group represented by Q, R, Y and Z is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples thereof include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the amino group include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino And so on.

The acylamino group represented by Q, R, Y and Z is 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. And examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

The aminocarbonylamino group represented by Q, R, Y and Z is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

The alkoxycarbonylamino group represented by Q, R, Y and Z is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

The aryloxycarbonylamino group represented by Q, R, Y and Z is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

The sulfamoylamino group represented by Q, R, Y and Z is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

The alkyl and arylsulfonylamino groups represented by Q, R, Y and Z are substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms And examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the alkylsulfonylamino group and arylsulfonylamino group include, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like. I can do it.

The alkylthio group represented by Q, R, Y and Z is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. Examples thereof include the same substituents as mentioned when the group is a group. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

The arylthio group represented by Q, R, Y and Z is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, and examples of the substituent include a group in which G can further have a substituent. And the same substituents as mentioned above. Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

The heterocyclic thio group represented by Q, R, Y and Z is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

The sulfamoyl group represented by Q, R, Y and Z is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. As an example of the substituent, the above G may further have a substituent. Examples thereof include the same substituents as mentioned when the group is a group. Examples of the sulfamoyl group include, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl. N- (N′-phenylcarbamoyl) sulfamoyl) and the like.

The alkyl and arylsulfinyl groups represented by Q, R, Y and Z 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. Examples of the same include the same substituents as those exemplified when G is a group which can further have a substituent. Examples of the alkyl and arylsulfinyl groups include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

The alkyl and arylsulfonyl groups represented by Q, R, Y, and Z 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. Examples of the same include the same substituents as those exemplified when G is a group which can further have a substituent. Examples of the alkyl and arylsulfonyl groups include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group represented by Q, R, Y and Z 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, carbon number A heterocyclic carbonyl group bonded to a carbonyl group with 4 to 30 substituted or unsubstituted carbon atoms is preferred, and examples of the substituent include when G is a group that can further have a substituent. The same substituents as mentioned above can be mentioned. Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

The aryloxycarbonyl group represented by Q, R, Y and Z is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

The alkoxycarbonyl group represented by Q, R, Y and Z is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. And the same substituents as mentioned when they are small groups. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

The carbamoyl group represented by Q, R, Y and Z is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. Examples thereof include the same substituents as mentioned when the group is a group. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

The phosphino group represented by Q, R, Y and Z is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. Examples thereof include the same substituents as mentioned when the group is a group. Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

The phosphinyl group represented by Q, R, Y, and Z is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. Examples thereof include the same substituents as mentioned when the group is a group. Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

The phosphinyloxy group represented by Q, R, Y and Z is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having.
Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

The phosphinylamino group represented by Q, R, Y and Z is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having.
Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

The silyl group represented by Q, R, Y and Z is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. Examples thereof include the same substituents as mentioned when the group is a group. Examples of the silyl group include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl and the like.

Examples of the azo group represented by Q, R, Y, and Z include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like. .

Examples of the imide group represented by Q, R, Y, and Z include N-succinimide and N-phthalimide.

When Q, R, X, Y and Z represent a divalent group, examples of the divalent group include an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene) and an alkenylene group (eg, ethenylene, propylene). Nylene), alkynylene groups (eg, ethynylene, propynylene), arylene groups (eg, phenylene, naphthylene), divalent heterocyclic groups (eg, 6-chloro-1,3,5-triazine-2,4-diyl groups) , Pyrimidine-2,4-diyl group, pyrimidine-4,6-diyl group, quinoxaline-2, 3-diyl group, pyridazine-3,6-diyl), -O-, -CO-, -NR '-( R 'is a hydrogen atom, an alkyl group or an aryl _{group), - S -, - SO} 2 -, - SO- , or a combination thereof (e.g., -NHCH ₂ CH ₂ NH -, - it is good is NHCONH-, etc.) Arbitrariness.

  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 described for G above.

  The alkyl group and aryl group for R ′ have the same meanings as the examples of the substituent for G.

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, a divalent heterocyclic group, -S-,- More preferably, it is SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.).

  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.

When Q, R, X, Y and Z represent a trivalent group, the trivalent group includes a trivalent hydrocarbon group, a trivalent heterocyclic group,> N-, or a divalent group thereof. (For example,> NCH ₂ CH ₂ NH—,> NCONH—, etc.).

  The total carbon number of the trivalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  In general formula (I), preferred examples of n are 1 or 2, with 2 being particularly preferred.

In the formula (I), substituent X is a Hammett's substituent constant .sigma.p value of 0.2 or more electron-withdrawing group, preferably, .sigma.p value of 0.30 or more electron-withdrawing group Preferably there is. The upper limit is 1.0 or less electron-withdrawing group.

Specific examples of X .sigma.p value of 0.20 or more electron-withdrawing group, an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono Group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group , Halogenated alkoxy groups, halogenated aryloxy groups, halogenated alkylamino groups, halogenated alkylthio groups, aryl groups substituted with other electron - withdrawing groups having a σp value of 0.20 or more, heterocyclic groups, halogens Atoms, azo groups, or selenocyanes Group. As examples of the above groups, those described in the above-mentioned items of Q, R, Y and Z can be applied.

Preferred examples of X include an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, and 7 to 18 carbon atoms. Aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, arylsulfinyl group having 6 to 18 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, 6 to 6 carbon atoms 18 arylsulfonyl groups, C 0-12 sulfamoyl groups, C 1-12 halogenated alkyl groups, C 1-12 halogenated alkyloxy groups, C 1-12 halogenated alkylthio groups, carbon number 7-18 halogenated aryloxy group, two or more σp0.20 more other electron-withdrawing groups substituted aryl group having 7 to 18 carbon atoms, Fine nitrogen atom, an oxygen atom or 5-8 membered ring having sulfur atom include a heterocyclic group having 1 to 18 carbon atoms.

  More preferably, they are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms.

  Particularly preferable as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and the most preferable one is a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms. It is.

  In the general formula (I), preferred examples of the substituent for Z are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group. Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

  Detailed examples of the substituent represented by Z are the same as the corresponding examples of the substituent described in the example of the heterocyclic group represented by G, and preferred examples are also the same.

  A particularly preferred substituent represented by Z is a substituted aryl group or a substituted heterocyclic group, and among these, a substituted aryl group is particularly preferred.

  In formula (I), preferred examples of the substituent for Q are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted aryl. A sulfonyl group is preferable, and a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group is preferable, and a hydrogen atom is particularly preferable among them.

  In general formula (I), R represents a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number of C4 to C4. A C12 heterocyclic group is preferable, and among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, a secondary or tertiary alkyl group is particularly preferable, and a t-butyl group is most preferable.

  In general formula (I), Y represents a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon. A C4 to C12 heterocyclic group is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1 to C8 and / or a branched alkyl group is preferable, and a hydrogen atom or a C1 to C8 alkyl group is particularly preferable. A hydrogen atom is most preferred.

  Regarding the preferred combination of substituents of the dye represented by the general formula (I) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the coloring matter represented by the general formula (I) of the present invention includes the following (A) to (G).

(I) G is preferably a 5- to 8-membered nitrogen-containing heterocycle, and particularly preferably an S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring. -A triazine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferred, and an S-triazine ring is most preferred.

(B) R is a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number of C4 to C12 heterocyclic group Among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, a secondary or tertiary alkyl group is particularly preferable, and a t-butyl group is most preferable.

(C) Particularly preferred as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and among them, a cyano group Or an alkylsulfonyl group having 1 to 12 carbon atoms, and a most preferred one is a cyano group.

(D) Y is a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number of C4 to C12. Of these, a heterocyclic group is preferable, and among them, a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms in total or a branched alkyl group is preferable, particularly a hydrogen atom or a C1 to C8 alkyl group is preferable, and a hydrogen atom is most preferable. preferable.

(E) Z is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, A substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred, and a particularly preferred substituent is a substituted aryl group or a substituted heterocyclic group, and among them, a substituted aryl group is particularly preferred.

(F) Q is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, particularly a hydrogen atom, A substituted or unsubstituted alkyl group or a substituted or unsubstituted acyl group is preferable, and a hydrogen atom is particularly preferable among them.

(G) n represents an integer of 1 to 3, preferably 1 or 2, and most preferably 2.

  Of the azo dyes represented by the above general formula (I), dyes represented by the following general formulas (1) to (5) are preferable.

Hereinafter, the general formula (1) will be described in detail.
General formula (1)

R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group.
The monovalent group represents a hydrogen atom or a monovalent substituent. As an example of a monovalent substituent, it is synonymous with the monovalent substituent example of R, X, Y, and Z in the said general formula (I), and its preferable example is also the same. m ₁ represents an integer of 0 to 3.

Hereinafter, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ will be described in more detail.

Examples of substituents for R ₁ and R ₂ are independently the same as the examples of R in the general formula (I), and preferred examples are also the same.

Examples of the substituent for Y ₁ and Y ₂ are each independently the same as the examples of Y in the general formula (I), and preferred examples are also the same.

Examples of the substituents for Z ₁ and Z ₂ are independently the same as the examples of Z in the general formula (I), and preferred examples are also the same.

Hereinafter, G and m ₁ will be described in more detail.

  G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

  Preferred examples of the 5- to 8-membered nitrogen-containing heterocycle represented by G are S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, and among them, S-triazine A ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring is more preferable, and an S-triazine ring is most preferable.

m ₁ represents an integer of 0 to 3, and when the —OM group can be substituted in the structure of the preferred example of the 5- to 8-membered nitrogen-containing heterocycle represented by G, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 is particularly preferable.

  Hereinafter, the M will be described in more detail.

  M represents a hydrogen atom or a cation.

The cation represented by M is an alkali metal ion, ammonium or a quaternary ammonium cation, and preferably Li, Na, K, NH ₄ , or NR ₄ . However, R is an alkyl group and an aryl group, and is the same as the examples of the alkyl group and aryl group represented by R and Y described above. Among them, preferable examples of the cation of M are Li, Na, K, or NH ₄ , and Li, Na, or K is particularly preferable.

  Regarding the preferred combination of substituents of the dye represented by the general formula (1) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the coloring matter represented by the general formula (1) of the present invention includes the following (A) to (F).

(I) R ₁ and R ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having a total carbon number of C1 to C12, substituted or unsubstituted aryl groups having a total carbon number of C6 to C18, or substituted or unsubstituted An unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a linear alkyl group or a branched alkyl group having a total carbon number of C1-C8 is preferable, and a secondary or tertiary alkyl group is particularly preferable, t A butyl group is most preferred.

_(B) X 1, _{X 2} may be the same or different substituent constant σp value of Hammett's preferably 0.20 or more electron-withdrawing group, further 0.30 or more electron-withdrawing group preferably, the upper limit is 1.0 or less electron-withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, Alternatively, a substituted or unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and further a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and a hydrogen atom is most preferable among them.

(D) Z ₁ and Z ₂ may be the same or different and are a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, An unsubstituted C4-C12 heterocyclic group having a total carbon number is preferred, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred, and a substituted aryl group is particularly preferred.

(E) G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and preferable examples of the 5- to 8-membered nitrogen-containing heterocycle include S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, and pyridine ring. , An imidazole ring, a pyrazole ring, or a pyrrole ring, among which an S-triazine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring is more preferable, and an S-triazine ring is most preferable.

(F) m ₁ represents an integer of 0 to 3, and when the —OM group is substitutable in the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G, 0 to 2 are preferred, Among them, 0 or 1 is preferable, and m ₁ = 1 is particularly preferable.

(G) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

Hereinafter, the general formula (2) will be described in detail.
General formula (2)

R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₁ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₂₁ and m ₂₂ each independently represents an integer of 0 to 3 .

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (2) will be described in more detail.

In the general formula (2), preferable examples of the substituents for R ₁ and R ₂ are the same as the examples of the substituents for R ₁ , R ₂ , Y ₁ , and Y ₂ described in the general formula (1), and are preferable. The example is the same.

In the general formula (2), preferable examples of the substituents of X ₁ and X ₂ are the same as the examples of the substituents of X ₁ and X ₂ described for formula (1), and preferred examples are also the same.

In the general formula (2), preferable examples of the substituents of Z ₁ and Z ₂ are the same as the examples of the substituents of Z ₁ and Z ₂ described for formula (1), and preferred examples are also the same.

Preferred examples of the general formula (2) in, G ₁ and G ₂ are the same as examples of G described for formula (1), and preferred examples are also the same.

In the general formula (2), m ₂₁ and m ₂₂ each independently represents an integer of 0 to 3, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ includes a —OM group. Is preferably 0 to 2, more preferably 0 or 1, and most preferably m ₂₁ = 1 and m ₂₂ = 1.

  In General formula (2), the preferable example of M is synonymous with the example of M demonstrated by the said General formula (1), and its preferable example is also the same.

In the general formula (2), preferable examples of the substituents of R ₁₁ and R ₁₂ are the same as the examples of the substituents of R ₁ , R ₂ , Y ₁ , and Y ₂ described in the general formula (1), and are preferable. Examples are -OM group (M is hydrogen atom or cation), substituted or unsubstituted amino group; alkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, substituted or unsubstituted carbon number Examples thereof include an alkylthio group having 1 to 12 and a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms.

In the general formula (2), the divalent linking group represented by L ₁ is an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group ( Examples, 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, pyrimidine-4, 6-diyl group, Kinokisarin 2,3-diyl group, pyridazine over 3,6-diyl), - O -, - CO -, - NR- (R is a hydrogen atom, an alkyl group or an aryl group), - S -, - SO 2 -, - SO-, or a combination thereof (e.g., _{-NHCH 2 CH 2 NH -, -} NHCONH- , etc.) is preferably.

  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 the substituents of _{R 1,} R 2, _{Y 1} and _{Y 2} in the general formula (1).

The alkyl group and aryl group of R are synonymous with the substituent examples of R ₁ , R ₂ , Y ₁ and Y _{2 in} the general formula (1).

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 a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.) and more preferably a.

  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.

  Regarding the preferred combination of substituents of the dye represented by the general formula (2) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the coloring matter represented by the general formula (2) of the present invention includes the following (i) to (h).

(I) R ₁ and R ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having a total carbon number of C1 to C12, substituted or unsubstituted aryl groups having a total carbon number of C6 to C18, or substituted or unsubstituted An unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a linear alkyl group or a branched alkyl group having a total carbon number of C1-C8 is preferable, and a secondary or tertiary alkyl group is particularly preferable, t A butyl group is most preferred.

_(B) X 1, _{X 2} may be the same or different substituent constant σp value of Hammett's preferably 0.20 or more electron-withdrawing group, further 0.30 or more electron-withdrawing group preferably, the upper limit is 1.0 or less electron-withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Z ₁ and Z ₂ may be the same or different and are a substituted or unsubstituted C1-C12 alkyl group having a total number of carbon atoms, a substituted or unsubstituted aryl group having a total carbon number of C6-C18, An unsubstituted C4-C12 heterocyclic group having a total carbon number is preferred, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred, and a substituted aryl group is particularly preferred.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₂₁ and m ₂₂ each independently represents an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₂₁ = 1 and m ₂₂ = 1 are particularly preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group (an alkylamino group having 1 to 12 carbon atoms, 6 carbon atoms) To an arylamino group having 1 to 18 carbon atoms), a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, among which an unsubstituted amino group and carbon number An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms is particularly preferable. Unsubstituted amino group, dialkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, or substituted or unsubstituted An alkylthio group having from 1 to 12 carbons are preferred.

(H) L ₁ is 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 a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.), more preferably an alkylene group having 10 or less carbon atoms, having 6 to 10 carbon It is preferably an arylene group, —S—, —SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.), particularly 10 carbon atoms. following alkylene _{group, -SCH 2 CH 2 S -,} - SCH 2 CH 2 CH 2 S- and is preferably.

Hereinafter, the general formula (3) will be described in detail.
General formula (3)

R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₂ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (3) will be described in more detail.

In the general formula _(3), preferable examples of the substituents of _{R 1, R 2, Y 1} , and _{Y 2, R} 1 described for Formula _(1), R 2, _{Y 1,} and _{Y 2} substituents Examples are the same, and preferred examples are also the same.

In the general formula (3), preferable examples of the substituents of X ₁ and X ₂ are the same as examples of the substituents of X ₁ and X ₂ described for formula (1), and preferred examples are also the same.

Preferred examples of the general formula (3) in, G ₁ and G ₂ are the same as examples of G described for formula (1), and preferred examples are also the same.

In the general formula (3), preferred examples of m ₃₁ and m ₃₂ are the same as the examples of m ₂₁ and m ₂₂ described in the general formula (2), and preferred examples are also the same.

  In General formula (3), the preferable example of M is the same as the example of M demonstrated by the said General formula (1), and its preferable example is also the same.

In the general formula _(3), preferable examples of the substituents of _{R 11} and _{R 12} are the same as the examples of the substituents of _{R 11, R 12} described for Formula (2), and preferred examples are also the same.

In the general formula (3), the divalent linking group represented by L ₂ has the same meaning as the example of L ₁ described in the general formula (2), and preferred examples are also the same.

  Regarding the preferred combination of substituents of the dye represented by the general formula (3) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the coloring matter represented by the general formula (3) of the present invention includes the following (A) to (H).

(I) R ₁ and R ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having a total carbon number of C1 to C12, substituted or unsubstituted aryl groups having a total carbon number of C6 to C18, or substituted or unsubstituted An unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a linear alkyl group or a branched alkyl group having a total carbon number of C1-C8 is preferable, and a secondary or tertiary alkyl group is particularly preferable, t A butyl group is most preferred.

_(B) X 1, _{X 2} may be the same or different substituent constant σp value of Hammett's preferably 0.20 or more electron-withdrawing group, further 0.30 or more electron-withdrawing group preferably, the upper limit is 1.0 or less electron-withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, Alternatively, a substituted or unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and further a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and a hydrogen atom is most preferable among them.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and 0 or 1 is preferable, and m ₃₁ = 1 and m ₃₂ = 1 are most preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group (an alkylamino group having 1 to 12 carbon atoms, 6 carbon atoms) To an arylamino group having 1 to 18 carbon atoms), a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, among which an unsubstituted amino group and carbon number An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms is particularly preferable. Unsubstituted amino group, dialkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, or substituted or unsubstituted An alkylthio group having from 1 to 12 carbons are preferred.

(H) L ₂ is 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 a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.), more preferably an alkylene group having 10 or less carbon atoms, having 6 to 10 carbon It is preferably an arylene group, —S—, —SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.), particularly 10 carbon atoms. following alkylene _{group, -SCH 2 CH 2 S -,} - SCH 2 CH 2 CH 2 S- and is preferably.

Hereinafter, Formula (4) will be described in detail.
General formula (4)

R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ and Z ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₃ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (4) will be described in more detail.

In the general formula (4), preferred examples of the substituents of _{Y 1,} and _{Y 2, R} 1 described for Formula _(1), R 2, _{Y 1,} and are the same as the examples of the substituents of _{Y 2,} The preferred examples are also the same.

In the general formula (4), preferred examples of the substituents of X ₁ and X ₂ are the same as examples of the substituents of X ₁ and X ₂ described for formula (1), and preferred examples are also the same.

Preferred examples of the general formula (4) in, G ₁ and G ₂ are the same as examples of G described for formula (1), and preferred examples are also the same.

In the general formula (4), preferred examples of m ₄₁ and m ₄₂ are the same as the examples of m ₂₁ and m ₂₂ described in the general formula (2), and preferred examples are also the same.

  In General formula (4), the preferable example of M is the same as the example of M demonstrated by the said General formula (1), and its preferable example is also the same.

In the general formula _(4), preferred examples of the substituents of _{R 11} and _{R 12} are the same as the examples of the substituents of _{R 11, R 12} described for Formula (2), and preferred examples are also the same.

In the general formula (4), examples of the divalent linking group represented by L ₃ are the same as the examples of L ₁ described for formula (2), and preferred examples are also the same.

  Regarding the preferred combination of substituents of the dye represented by the general formula (4) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the coloring matter represented by the general formula (4) of the present invention includes the following (i) to (h).

(I) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, Alternatively, a substituted or unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and a hydrogen atom is most preferable among them.

_(B) X 1, _{X 2} may be the same or different substituent constant σp value of Hammett's preferably 0.20 or more electron-withdrawing group, further 0.30 or more electron-withdrawing group preferably, the upper limit is 1.0 or less electron-withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Z ₁ and Z ₂ may be the same or different and are a substituted or unsubstituted C1-C12 alkyl group having a total number of carbon atoms, a substituted or unsubstituted aryl group having a total carbon number of C6-C18, An unsubstituted C4-C12 heterocyclic group having a total carbon number is preferred, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred, and a substituted aryl group is particularly preferred.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In such a case, 0 to 2 are preferable, and 0 or 1 is preferable, and m ₄₁ = 1 and m ₄₂ = 1 are most preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group (an alkylamino group having 1 to 12 carbon atoms, 6 carbon atoms) To an arylamino group having 1 to 18 carbon atoms), a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, among which an unsubstituted amino group and carbon number An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms is particularly preferable. Unsubstituted amino group, dialkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, or substituted or unsubstituted An alkylthio group having from 1 to 12 carbons are preferred.

(H) L ₃ is 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 a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.), more preferably an alkylene group having 10 or less carbon atoms, having 6 to 10 carbon It is preferably an arylene group, —S—, —SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.), particularly 10 carbon atoms. following alkylene _{group, -SCH 2 CH 2 S -,} - SCH 2 CH 2 CH 2 S- and is preferably.

Hereinafter, Formula (5) will be described in detail.
General formula (5)

R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₄ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (5) will be described in more detail.

In the general formula _(5), R _1, preferred examples of the substituents of R 2, _{Y 1} and _{Y 2} are, _R 1 described for Formula _{(1), R 2, Y} 1, and examples of the substituents of _{Y 2} The preferred examples are also the same.

In the general formula (5), preferable examples of the substituents of Z ₁ and Z ₂ are the same as examples of the substituents of Z ₁ and Z ₂ described for formula (1), and preferred examples are also the same.

Preferred examples of the general formula (5) in, G ₁ and G ₂ are the same as examples of G described for formula (1), and preferred examples are also the same.

In the general formula (5), preferable examples of m ₅₁ and m ₅₂ are the same as the examples of m ₂₁ and m ₂₂ described in the general formula (2), and preferable examples are also the same.

  In General formula (5), the preferable example of M is the same as the example of M demonstrated by the said General formula (1), and its preferable example is also the same.

In the general formula _(5), preferable examples of the substituents of _{R 11} and _{R 12} are the same as the examples of the substituents of _{R 11} and _{R 12} described for formula (2), and preferred examples are also the same.

In the general formula (5), examples of the divalent linking group represented by L ₄ are the same as the examples of L ₁ described for formula (2), and preferred examples are also the same.

  Regarding the preferred combination of substituents of the dye represented by the general formula (5) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the coloring matter represented by the general formula (5) of the present invention includes the following (i) to (h).

(I) R ₁ and R ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having a total carbon number of C1 to C12, substituted or unsubstituted aryl groups having a total carbon number of C6 to C18, or substituted or unsubstituted An unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a linear alkyl group or a branched alkyl group having a total carbon number of C1-C8 is preferable, and a secondary or tertiary alkyl group is particularly preferable, t A butyl group is most preferred.

(B) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, Alternatively, a substituted or unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and further a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and a hydrogen atom is most preferable among them.

(C) Z ₁ and Z ₂ may be the same or different and are substituted or unsubstituted alkyl groups having a total carbon number of C1 to C12, substituted or unsubstituted aryl groups having a total carbon number of C6 to C18, or substituted Alternatively, an unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is more preferable, and a substituted aryl group is most preferable.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and 0 or 1 is preferable, and m ₅₁ = 1 and m ₅₂ = 1 are most preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group; an alkylamino group having 1 to 12 carbon atoms, and 6 carbon atoms To an arylamino group having 1 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, and a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms. Among them, an unsubstituted amino group and an alkylthio group having 1 to 12 carbon atoms are preferable. Are preferably an alkylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms. An amino group, a dialkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, or a substituted or unsubstituted carbon number 12 alkylthio group are preferable.

(Chi) L ₄ represents a divalent and Hammett's substituent constant σp value of 0.20 or more electron-withdrawing groups linking group, preferably of 0.30 or more electron-withdrawing group, the upper limit is 1.0 or less of the electron-withdrawing group. Among them, an alkylsulfonyl group having 1 to 12 carbon atoms: {—SO ₂ — (CH ₂ ) n —O ₂ S—; an integer where n = 1 to 10}, an arylsulfonyl group having 6 to 18 carbon atoms: {— SO ₂ —Ar—O ₂ S—; Ar is preferably a substituted or unsubstituted aryl group, and most preferably an alkylsulfonyl group having 1 to 12 carbon atoms: {—SO ₂ — (CH ₂ ) n—O ₂ S-; n = integer of 1 to 5.}

Of the azo dyes represented by the general formula (1), a dye represented by the general formula (6) is preferable.
General formula (6)

  Hereinafter, Formula (6) will be described in detail.

R ₁ , R ₂ , Y ₁ , and Y _{2 each} represent a monovalent group, and X ₁ and X ₂ each independently represent an electron - withdrawing group having a Hammett σp value of 0.20 or more. Z ₁ and Z ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted An aryl group or a substituted or unsubstituted heterocyclic group is shown. M represents a hydrogen atom or a cation.

Hereinafter, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , Z ₂ and M will be described in detail.

Examples of the substituents of R _{1, R} 2, _{Y 1,} and _{Y 2} are preferably the same as the examples of the substituents of the general formula (1) _R 1 described _in, R 2, _{Y 1,} and _{Y 2} The example is the same.

Examples of the substituents of X ₁ and X ₂ are the same as examples of the substituents of X ₁ and X ₂ described for Formula (1) and preferred examples thereof are also the same.

Examples of the substituents of Z ₁ and Z ₂ are the same as examples of the substituents of Z ₁ and Z ₂ described for Formula (1) and preferred examples thereof are also the same.

  The example of M is the same as the example of M demonstrated in the said General formula (1), and its preferable example is also the same.

  Regarding the preferred combination of substituents of the dye represented by the general formula (6) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the coloring matter represented by the general formula (6) of the present invention includes the following (A) to (E).

(I) R ₁ and R ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having a total carbon number of C1 to C12, substituted or unsubstituted aryl groups having a total carbon number of C6 to C18, or substituted or unsubstituted An unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a linear alkyl group or a branched alkyl group having a total carbon number of C1-C8 is preferable, and a secondary or tertiary alkyl group is particularly preferable, t A butyl group is most preferred.

_(B) X 1, _{X 2} may be the same or different substituent constant σp value of Hammett's preferably 0.20 or more electron-withdrawing group, further 0.30 or more electron-withdrawing group preferably, the upper limit is 1.0 or less electron-withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, Alternatively, a substituted or unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and further a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and a hydrogen atom is most preferable among them.

(D) Z ₁ and Z ₂ may be the same or different and are a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, An unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferable, and a substituted aryl group is particularly preferable.

(E) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

  In the present invention, when the compounds represented by the general formulas (I), (1), (2), (3), (4), (5) and (6) require hydrophilicity, It preferably has 2 or more ionic hydrophilic groups, more preferably 2 to 10 ionic hydrophilic groups, and particularly preferably 3 to 6 ionic hydrophilic groups.

  However, when water is not used as a medium, it does not have to have an ionic hydrophilic group.

The ionic hydrophilic group may be any as long as it is an ionic dissociation group.
Specific examples include a sulfo group, a carboxyl group (including salts thereof), a hydroxyl group (may be a salt), a phosphono group (may be a salt), or quaternary ammonium.

A sulfo group, a carboxyl group, or a hydroxyl group (including salts thereof) is preferable.
When the ionic hydrophilic group is a salt, preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium), among them Alkali metals are preferred. In particular, a lithium salt is preferred for a sulfo group, and a sodium salt and / or a potassium salt is preferred for a carboxy group.

In the case of water-soluble dyes represented by the general formulas (I), (1), (2), (3), (4), (5) and (6), from the viewpoint of color reproducibility, It preferably has a maximum absorption wavelength (λmax) of 380 to 490 nm in H ₂ O, more preferably has a λmax of 400 to 480 nm, and particularly preferably has a λmax of 420 to 460 nm.

  Specific examples of the dyes represented by the general formulas (I), (1), (2), (3), (4), (5), and (6) (exemplary dyes DYE-1 to 26) are shown below. The dye used in the invention is not limited to the following examples.

  Moreover, although the structure of the following specific examples is shown with the form of a free acid, it cannot be overemphasized that you may use as arbitrary salts.

  Preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, or organic cations (eg, pyridinium, tetramethylammonium, guanidinium).

Next, the compound represented by the general formula (7) in the present invention will be described in detail.
General formula (7)

  The compound represented by the general formula (7) includes a compound, a salt thereof, and a hydrate thereof.

  The compound represented by the general formula (7) is a novel compound useful as a functional material for organic photoconductive materials, optical recording materials, pharmaceuticals and agricultural chemicals, in addition to dyes and pigments. It is useful as a synthetic intermediate for azomethine dyes.

In the general formula (7), R ₃ and R ₄ are each independently synonymous with R ₁ and R ₂ represented by the general formula (2), and preferred examples are also the same.
In the general formula (7), P ₁ and P ₂ each independently represent a hydrogen atom or a leaving group.

In the present specification, the leaving group means a group that is eliminated by a chemical reaction, for example, a group that is eliminated by a coupling reaction with a diazonium salt, or an phenylenediamine derivative oxidized to easily cause an addition / elimination reaction. It is a group. Preferred examples of P ₁ and P ₂ include a hydrogen atom, a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, or an arylthio group, among which a hydrogen atom or a halogen atom is preferable, and among them, a hydrogen atom Is preferred.

  The method for synthesizing the dye and intermediate of the present invention will be described in detail.

<1> Synthesis of coupling component:
The coupling component used in the synthesis of the coloring matter of the present invention (pigment intermediate that reacts with a diazonium salt to induce an azo dye) is preferably a compound represented by the following general formula (8).
General formula (8)

  The substituents R, G and Q in the general formula (8) are each independently synonymous with R, G and Q in the general formula (I), and preferred examples are also the same.

  N in the said General formula (8) represents the integer of 1-3.

  P represents a hydrogen atom or a leaving group. The leaving group means a group that is eliminated by a chemical reaction, for example, a group that is eliminated by a coupling reaction with a diazonium salt, or a group that easily causes an addition / elimination reaction with an oxidized form of a phenylenediamine derivative. Preferred examples of P include a hydrogen atom, a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, or an arylthio group. Among these, a hydrogen atom or a halogen atom is preferable, and a hydrogen atom is most preferable.

A more preferred example of the coupling component represented by the general formula (8) is a compound represented by the following general formula (9), a salt or a hydrate thereof.
General formula (9)

  The substituents R, G and P in the general formula (9) have the same meanings as R, G and P in the general formula (8), and preferred examples are also the same. In addition, the compound represented by the general formula (7) is included in the compound represented by the general formula (9).

M in the general formula (9) represents a hydrogen atom or a cation.
When M represents a cation, it is synonymous with M in General formula (1), and its preferable example is also the same.

A particularly preferable example of the coupling component represented by the general formula (9) is a compound represented by the following general formula (10), a salt or a hydrate thereof.
General formula (10)

  The substituent R in the general formula (10) is independently the same as R in the general formula (8), and preferred examples are also the same.

  M in the general formula (10) has the same meaning as M in the general formula (9), and preferred examples thereof are also the same.

  Hereinafter, a method for synthesizing the coupling component represented by the general formula (9) will be described.

  The compound represented by the general formula (9) can be obtained, for example, according to the following steps.

(A) a step of allowing a base to act on a mixture of an organic compound (α) having a halogen atom detachable with respect to hydrazine and water; and (b) a reaction solution obtained in the step (a) and hydrazine. After obtaining the hydrazine derivative from the mixing step, (c) the step of reacting the hydrazine derivative obtained in (b) above with the acylacetonitrile compound in the presence of an acid and an organic solvent is represented by the general formula (9). Compound; (hereinafter referred to as 5-aminopyrazole compound).

  Examples of the organic compound (α) include cyanuric chloride, 2-chloropyrimidine, 2,4-chloropyrimidine, 2,4,6-trichloropyrimidine, 3-chloropyridazine, 3,5-dichloropyridazine, 5-chloropyrazole, Or 2-chloroimidazole is mentioned. Preferred are cyanuric chloride, 2,4,6-trichloropyrimidine, or 3,5-dichloropyridazine, 2-chloroimidazole. Among them, cyanuric chloride and 2,4,6-trichloropyrimidine are preferable, and in particular, cyanuric chloride. Is most preferred.

  First, as the step (a), a base is allowed to act on a mixture of the organic compound (α) and water. In the present invention, water can be used in this way as a preferred reaction solvent for the production of hydrazine derivatives. The amount of water used relative to the organic compound (α) is preferably 0.5 to 50 times, more preferably 1 to 20 times.

  In the present invention, the organic compound (α) is preferably dispersed in water, but depending on the type of the organic compound (α), it can be in an aqueous solution state.

  Further, the solvent of the mixture of the organic compound (α) and water is mainly composed of water as described above (10 to 100% by mass, preferably 50 to 100% by mass of the total solvent). These solvents can be used. Examples of such a solvent include dimethylformamide, dimethylacetamide, dimethyl sulfoxide and the like.

Bases include inorganic bases and organic bases. Examples of the inorganic base include sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium acetate, sodium acetate, lithium acetate and the like, preferably sodium hydroxide, sodium bicarbonate, Or it is potassium carbonate, More preferably, it is sodium hydrogencarbonate or sodium hydroxide. Examples of the organic base include ammonia, hydrazine, triethylamine, diazobicycloundecene, pyridine, 2,6-dimethylpyridine, dimethylaminopyridine, etc., preferably ammonia, hydrazine, triethylamine, or pyridine, and more preferably ammonia. Or hydrazine. As the usage-amount of a base, 0.05-30.0 equivalent is preferable with respect to the usage-amount of an organic compound ((alpha)), More preferably, it is 0.5-15.0 equivalent.

  As reaction temperature, 5 to 80 degreeC is preferable and 10 to 60 degreeC is more preferable.

  The reaction time is preferably 30 minutes to 6 hours, and more preferably 1 hour to 3 hours.

  Subsequently, as the step (b), the reaction solution obtained in the step (a) and hydrazine are mixed and reacted to produce a hydrazine derivative. The ratio of addition of the organic compound (α) and hydrazine is, for example, preferably 1: 1 to 1:20, more preferably 1: 2 to 1:10 as the former: the latter (molar ratio).

  The reaction temperature in the step (b) is preferably 0 ° C to 90 ° C, more preferably 0 ° C to 80 ° C, and further preferably 0 ° C to 65 ° C. If it is less than 0 ° C., the reaction rate is remarkably slow and the time required for the synthesis becomes remarkably long, which is not economical. When synthesis is performed at a high temperature exceeding 90 ° C., the amount of by-products increases, which is not preferable. .

  The reaction time in step (b) is preferably from 30 minutes to 300 minutes, more preferably from 30 minutes to 200 minutes, still more preferably from 30 minutes to 150 minutes.

A reaction scheme in the case of using cyanuric chloride as the organic compound (α) and sodium hydrogen carbonate as the base is shown below.

  The hydrazine derivative can synthesize a 5-aminopyrazole compound by reacting with an acylacetonitrile compound in the presence of an acid and an organic solvent.

  This hydrazine derivative may be manufactured according to the present application or manufactured by other than the present application.

  As an organic solvent, in particular, an intermediate obtained by adding a hydrazine derivative and an acylacetonitrile compound (hereinafter simply referred to as an intermediate) is dissolved, and a 5-aminopyrazole compound is precipitated from the reaction system to generate a reaction subcomponent. A solvent that suppresses the above is desired.

  In the present invention, the organic solvent is a solvent that does not cause a liquid separation phenomenon during the reaction and exhibits a uniform solution with the solvent. For example, alcoholic organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol, amyl alcohol, ketone organic solvents such as acetone, methyl ethyl ketone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene Diol-based organic solvents such as glycol and 1,3-propanediol, ether-based organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol diethyl ether, tetrahydrofuran, dioxane, acetonitrile, and the like. May be a mixture of two or more.

  Preferably, the organic solvent has a polarity parameter (ET) value of 40 or more. Among these, a glycol solvent having two or more hydroxyl groups in the solvent molecule, or an alcohol solvent having 3 or less carbon atoms, preferably an alcohol solvent having 2 or less carbon atoms is preferable. These mixed solvents are also included.

As the organic solvent, an organic solvent having a hydroxyl group is particularly preferable. More preferable examples of alcohol include methanol and ethanol. The oligo - (especially di- - and tri -) and poly -C 2 _-C 4 _- glycols such as alkylene glycols are also suitable. Also advantageous are compounds based on ethylene. Examples include ethylene glycol, 1,2- and 1,3-propylene glycol, diethylene glycol, butylene glycol, di-, tri- and tetraethylene glycol, di-, tri- and tetrapropylene glycol, polyethylene- and polypropylene glycol, glycerin Etc.

  More preferable examples include methanol, ethylene glycol, diethylene glycol, triethylene glycol, polypropylene glycol, propylene glycol, dipropylene glycol, glycerin, a 1: 2 (v / v) mixed solvent of ethylene glycol and diethylene glycol, propylene glycol and triethylene glycol. 3: 1 (v / v), methanol and ethylene glycol 1: 2 to 3 (v / v), methanol and triethylene glycol 1: 2 to 5 (v / v). The usage-amount of a solvent is 1-100 mass times of the compound represented by the said General formula (1), Preferably it is 1-50 mass times, More preferably, it is 1-20 mass times.

  The acid is not particularly limited, but inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid, and organic acids such as methanesulfonic acid are also effective. The amount used is 1 to 100 times, preferably 1 to 20 times, more preferably 1 to 10 times the amount of the hydrazine derivative. If the amount of the acid is small, the solubility of the intermediate is poor and the reaction time becomes long. If the amount of the acid is too large, a large amount of subcomponents are generated, which may lead to a deterioration in yield.

  Examples of the acyl group in the acylacetonitrile compound include an acetyl group, a pivaloyl group, an isopropylcarbonyl group, a phenethylcarbonyl group, a 2-naphthylcarbonyl group, and a 2-pyridylcarbonyl group. Particularly preferred is an acetyl group, a pivaloyl group, an isopropylcarbonyl group, or a phenethylcarbonyl group.

  When the number of moles of hydrazine in the hydrazine derivative is 1, the acylacetonitrile compound is preferably 1 to 5, more preferably 1 to 3.

  The reaction temperature of the hydrazine derivative and the acylacetonitrile compound is preferably 0 ° C to 120 ° C, more preferably 0 ° C to 100 ° C, and further preferably 0 ° C to 75 ° C.

  The reaction time is preferably 1 hour to 20 hours, more preferably 1 hour to 15 hours, and still more preferably 1 hour to 10 hours.

  A reaction scheme of a series of steps of a method for producing a hydrazine derivative of the present invention and a method for producing a 5-aminopyrazole compound using the hydrazine derivative produced thereby is shown below. In the following scheme, cyanuric chloride was used as the starting organic compound (α), sodium hydrogen carbonate as the base, pivaloyl acetonitrile as the acylacetonitrile compound, hydrochloric acid as the acid, and a mixed solvent of methanol and ethylene glycol as the organic solvent. However, the present invention is not limited to this.

<2> Synthesis of diazo component:
The diazo component (a dye intermediate for deriving a diazonium salt) used in synthesizing the dye of the present invention is preferably a compound represented by the following general formula (11).
Formula (11)

  The substituents X, Y and Z in the general formula (11) have the same meanings as X, Y and Z in the general formula (I), and preferred examples thereof are also the same.

  The compound represented by the general formula (11) can be obtained, for example, according to the following reaction formula. In the formula, R represents a lower alkyl group, and -OW represents a leaving group.

<3> Synthesis of the azo dye of the present invention:
The dye of the present invention can be synthesized, for example, by subjecting a diazonium salt prepared by a known method to a diazo component of the general formula (11) and an azo coupling reaction with the coupling components of the general formulas (8) and (9).

  The diazonium salt preparation and coupling reaction can be carried out by conventional methods.

  The diazonium salt preparation of the general formula (11) is prepared, for example, in a reaction medium containing an acid (for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.) Conventional diazonium salt preparation methods using nitrous acid, nitrite or nitrosylsulfuric acid can be applied.

  More preferable examples of the acid include a case where acetic acid, propionic acid, methanesulfonic acid, phosphoric acid and sulfuric acid are used alone or in combination, and among them, a combined system of acetic acid and / or propionic acid and sulfuric acid is particularly preferable.

  Preferable examples of the reaction medium (solvent) include organic acids and inorganic acids, and phosphoric acid, sulfuric acid, acetic acid, propionic acid, and methanesulfonic acid are particularly preferable. Among these, acetic acid and / or propionic acid are preferable.

  As an example of a preferable nitrosonium ion source, a diazonium salt can be stably and efficiently prepared by using nitrosylsulfuric acid in the above-mentioned preferable acid-containing reaction medium.

  0.5-50 mass times is preferable, as for the usage-amount of the solvent with respect to the diazo component of General formula (11), More preferably, it is 1-20 mass times, and 3-10 mass times is especially preferable.

  In the present invention, the diazo component of the general formula (11) may be in a state of being dispersed in a solvent, or may be in a solution state depending on the kind of the diazo component.

  The amount of nitrosonium ion source used is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, particularly 1.00 to 1.10 equivalents, relative to the diazo component. Is preferred.

  The reaction temperature is preferably -15 ° C to 30 ° C, more preferably -10 ° C to 10 ° C, and further preferably -5 ° C to 5 ° C. Less than −10 ° C. is not economical because the reaction rate is remarkably slow and the time required for the synthesis is remarkably increased, and it is preferable to synthesize at a high temperature exceeding 30 ° C. because the amount of by-products increases. Absent.

  The reaction time is preferably 30 minutes to 300 minutes, more preferably 30 minutes to 200 minutes, and still more preferably 30 minutes to 150 minutes.

  The coupling reaction (azo dyeing step) can be carried out in an acidic reaction medium to a basic reaction medium, but the azo dye of the present invention is preferably carried out in an acidic to neutral reaction medium, particularly When carried out in an acidic reaction medium, decomposition of the diazonium salt can be suppressed and the azo dye can be efficiently induced.

  As a preferable example of the reaction medium (solvent), an organic acid, an inorganic acid, or an organic solvent can be used, but an organic solvent is particularly preferable, and a solvent that does not cause a liquid separation phenomenon during the reaction and presents a uniform solution with the solvent. preferable. For example, alcoholic organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol, amyl alcohol, ketone organic solvents such as acetone, methyl ethyl ketone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene Diol-based organic solvents such as glycol and 1,3-propanediol, ether-based organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol diethyl ether, tetrahydrofuran, dioxane, acetonitrile, and the like. May be a mixture of two or more.

  Preferably, the organic solvent has a polarity parameter (ET) value of 40 or more. Among them, a glycol solvent having two or more hydroxyl groups in the solvent molecule, or an alcohol solvent having 3 or less carbon atoms, preferably an alcohol solvent having 2 or less carbon atoms (for example, methanol, ethylene glycol) is used. preferable. These mixed solvents are also included.

  The amount of the solvent used is preferably 1 to 100 times by mass, more preferably 1 to 50 times, more preferably 2 to 10 times by mass that of the coupling component represented by the general formulas (8) and (9). It is.

  In the present invention, the coupling components of the general formulas (8) and (9) may be dispersed in a solvent, or may be in a solution state depending on the type of coupling component.

  The amount of the coupling component used is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, particularly 1.00 to 1.50, based on the azo coupling site. It is preferable that it is equivalent.

  The reaction temperature is preferably -30 ° C to 30 ° C, more preferably -15 ° C to 10 ° C, and further preferably -10 ° C to 5 ° C. Less than −30 ° C. is not economical because the reaction rate is remarkably slow and the time required for synthesis becomes remarkably long. In addition, synthesis at a high temperature exceeding 30 ° C. is preferable because the amount of by-products increases. Absent.

  The reaction time is preferably 30 minutes to 300 minutes, more preferably 30 minutes to 200 minutes, and still more preferably 30 minutes to 150 minutes.

  In the method for synthesizing the azo dye of the present invention, the product (azo dye) obtained by these reactions can be used with or without purification after being treated in accordance with a post-treatment method of a normal organic synthesis reaction. .

That is, for example, an operation of purifying the product liberated from the reaction system without purification, or by recrystallization, salt formation, column chromatography (for example, gel permeation chromatography (SEPHADEX ^™ LH-20: manufactured by Pharmacia), etc. It can be performed alone or in combination.

  Further, after completion of the reaction, the reaction solvent is distilled off, or it is poured into water or ice without distilling off, and the product liberated without neutralization or without neutralization is purified or recrystallized, The operation of purification by salt formation, column chromatography or the like can be performed alone or in combination and then used.

  After completion of the reaction, the reaction solvent is distilled off, or it is neutralized by putting it in water or ice without distilling it, or purifying what is extracted with an organic solvent / aqueous solution without neutralization. Without purification, or after performing the operations of crystallization, salt formation, and column chromatography, either alone or in combination, can also be used.

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.
The present invention can also be applied to a solid-state image pickup device such as a CCD, a color filter for recording / reproducing a color image used in a display such as an LCD or PDP, and a dyeing solution for dyeing various fibers.
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. The ink of the present invention may contain other additives as necessary 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, Known additives (described in JP-A No. 2003-306623) such as a foaming agent, a viscosity modifier, a dispersant, a dispersion stabilizer, a rust inhibitor, and a chelating agent can be used. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an 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.

  When the dye of the present invention is dispersed in an aqueous medium, JP-A Nos. 11-286637, 2001-240763 (Japanese Patent Application No. 2000-78491), JP-A No. 2001-262039 (Japanese Patent Application No. 2000-80259), JP As described in Japanese Patent Application No. 2001-247788 (Japanese Patent Application No. 2000-62370), colored fine particles containing a dye and an oil-soluble polymer are dispersed in an aqueous medium, or Japanese Patent Application Laid-Open No. 2001-262018 (Japanese Patent Application No. 2000-78454) and Japanese Patent Application Laid-Open No. 2001-2001. It is preferable to disperse the dye of the present invention dissolved in a high-boiling organic solvent in an aqueous medium as described in JP-A-240763 (Japanese Patent Application No. 2000-78491) and JP-A No. 2001-335734 (Japanese Patent Application No. 2000-203856). The specific method for dispersing the coloring matter 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 should preferably be those described in the above-mentioned patent documents. Can do. 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. Regarding the method for preparing the ink for ink jet recording, in addition to the above-mentioned patent documents, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, 7-118584, Details are described in JP-A Nos. 11-286637 and 2001-271003 (Japanese Patent Application No. 2000-87539), and can also be used for preparing the ink for ink jet 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 those described in JP-A No. 2003-306623. In addition, the said water miscible organic solvent may use 2 or more types together.

  The pigment of the present invention is preferably contained in an amount of 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.2 parts by mass or more and 10 parts by mass or less, in 100 parts by mass of the ink for inkjet recording of the present invention. More preferably, the content is 0.5 to 9 parts by mass. In addition, the inkjet ink of the present invention may be used in combination with another pigment together with the pigment 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, the ink for inkjet recording in the present invention can simultaneously use another yellow dye in addition to the coloring matter in the present invention. As the applicable yellow dye, applicable magenta dye, and applicable cyan dye, any of them can be used, but each dye described in paragraph Nos. 0090 to 0092 of JP-A-2003-306623 can be used. . Applicable black materials include disazo, 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 for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as 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 10-337947, 10-217597, 10-337947, etc. Form images on inkjet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. To do. The description of paragraph numbers 0093 to 0105 of JP-A No. 2003-306623 can be applied as the ink jet recording method of the present invention.

  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, and therefore the addition location may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, JP 2002-166638 (Japanese Patent Application 2000-363090), JP 2002-121440 (Japanese Patent Application 2000-315231), JP 2002-154201 (Japanese Patent Application 2000-354380), JP 2002-144696 ( The methods described in Japanese Patent Application No. 2000-343944), Japanese Patent Application Laid-Open No. 2002-080759 (Japanese Patent Application No. 2000-268952), Japanese Patent Application No. 2000-299465, and Japanese Patent Application No. 2000-297365 can be preferably used.

[Color toner]
Although there is no restriction | limiting in particular in content of the pigment | dye of this invention in 100 mass parts of color toners of this invention, it is preferable to contain 0.1 mass part or more, 1-20 mass parts is more preferable, 2-10 mass parts is preferable. Most preferably it contains.
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 recording (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 preferably used.

  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-4-175653. 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 for introducing the coloring matter of the present invention into a color filter. Preferred methods are described in JP-A-4-175533 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 is formed according to a conventional method, and an RGB primary color system or Y, M, C complementary color system color filter can be obtained. In the case of a color filter, although there is no restriction | limiting of the usage-amount of pigment | dye, 0.1-50 mass% is preferable.

  Regarding the thermosetting resin, quinonediazide compound, crosslinking agent, and solvent used in this case, and those used, those described in the above-mentioned patent documents can be preferably used.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

  As a representative example, a method for synthesizing a dye (DYE-11) will be described.

(1) Synthesis of compound b:
25.5 g of sodium hydrogen carbonate and 150 mL of ion-exchanged water were heated to 40 ° C., and 25.0 g of cyanuric chloride (Tokyo Chemicals) was added in 10 divided portions every 10 minutes and stirred for 1 hour. The solution was added dropwise to a mixed solution (8 ° C.) of 52.8 mL of hydrazine and 47 mL of ion exchange water so that the internal temperature did not exceed 10 ° C. The internal temperature was raised to 50 ° C. and stirred for 30 minutes. The precipitated crystals were filtered to obtain 23.4 g of compound b (hydrazine derivative: mp> 300 ° C.). The yield was 94.7%.

(2) Synthesis of compound c:
35.0 g of compound b (hydrazine derivative) was suspended in 420 mL of ethylene glycol and stirred at an internal temperature of 50 ° C. Concentrated hydrochloric acid 59 mL, followed by 60.1 g of pivaloylacetonitrile (Tokyo Chemicals) were added and stirred at 50 ° C. for 10 hours. Concentrated hydrochloric acid (95 mL) and methanol (145 mL) were added, and the mixture was further stirred for 8 hours. After cooling to room temperature, the precipitated crystals were separated by filtration to obtain 81.6 g of compound c (5-aminopyrazole derivative: mp = 233-235 ° C.). The yield was 94.2%. ¹ H-NMR (DMSO-d6), δ value TMS standard: 1.2 to 1.3 (18H, s))

(3) Synthesis of compound e:
90.57 g of compound d (Tokyo Chemicals) was suspended in 500 ml of H ₂ O, and after cooling with 130 ml of concentrated hydrochloric acid, the internal temperature was cooled to 5 ° C. or lower. Next, 36.23 g of sodium nitrite and 70 ml of an aqueous solution were added dropwise at an internal temperature in the range of 4 to 6 ° C., and the mixture was further stirred at an internal temperature of 5 ° C. or lower for 30 minutes. Next, 159 g of sodium sulfite and 636 ml of H ₂ O were injected while maintaining the internal temperature at 20 ° C. or lower, and further 250 ml of concentrated hydrochloric acid was injected at an internal temperature of 25 ° C., followed by stirring at an internal temperature of 90 ° C. for 1 hour. After cooling the internal temperature to room temperature, the mixture was filtered, washed with 200 ml of water and air-dried to obtain 80.0 g of compound e.

(4) Synthesis of compound f:
28 ml of triethylamine was added dropwise to 23.3 g of compound e and 209 ml of ethanol suspension at room temperature, and 12.2 g of ethoxymethylenemalononitrile (ALDRICH product) was added in portions, refluxed for 3 hours, cooled to room temperature, filtered, and 400 ml of isopropyl After washing with alcohol and drying, 23.57 g of compound f was obtained.

(5) Synthesis of DYE-11:
Acetic acid (145.56 mL) was poured into sulfuric acid (32.4 mL) at an internal temperature of 4 ° C. or lower, and 40% nitrosyl sulfuric acid (15.9 mL) (ALDRICH product) was added dropwise with stirring at an internal temperature of 7 ° C. or lower.
32.4 g of compound f was added in portions and stirred at the same temperature for 60 minutes while stirring at an internal temperature of 10 ° C., and then 1.88 g of compound C in which 1.83 g of urea was added to the reaction mixture was added to 470 ml of methanol. To the suspended solution, a diazonium salt was added dropwise at an internal temperature <0 ° C., and the mixture was stirred as it was for 30 minutes, and then the internal temperature of the reaction solution was raised to room temperature, followed by filtration, methanol washing and H ₂ O washing. Thus, crude crystals were obtained. Subsequently, the crude crystals were suspended in 400 ml of methanol, stirred under reflux for 1 hour, cooled to room temperature, filtered, washed with methanol, washed with water, washed with methanol, dried overnight at 75 ° C., and then free acid form of DYE-11. 34.4 g of crystals were obtained. The obtained crystals were adjusted to 10 wt% aq (at 25 ° C .: pH≈8.3: KOHaq preparation), IPA was added at an internal temperature of 50 ° C., followed by crystallization, cooling, filtration, IPA washing, and drying. 35 g of DYE-11 (potassium salt) was obtained.
λmax = 436.4 nm (H ₂ O), ε: 3.53 × 10 ⁴ (dm ³ .cm / mol)

Examples of synthesis of the dye of the present invention are shown below. By applying the method for synthesizing the dye (DYE-11), other dyes can be synthesized in the same manner. Table 1 shows the λmax and ε values of the synthesized dye in H ₂ O. The inside of Dye-No () is an example of a counter cation of an ionic hydrophilic group.

  After adding ultrapure water (resistance value of 18 MΩ or more) to the following components to make 1 liter, the mixture was stirred for 1 hour while heating at 50 to 60 ° C. Thereafter, the mixture was filtered under reduced pressure through a microfilter having an average pore diameter of 0.25 μm to prepare a yellow ink liquid Y-101.

[Yellow ink Y-101 prescription]
(Solid content)
Yellow dye of the present invention (DYE-11 potassium salt) 50 g / l
Proxel XL2 (S) (Avecia) 5g / l
Urea 10g / l
(Liquid component)
Triethylene glycol monobutyl ether (DGB) 101g / l
Glycerin (GR) 118g / l
Triethylene glycol (DEG) 95g / l
2-pyrrolidone 20g / l
Triethanolamine (TEA) 10g / l
Surfynol 465 (SW) (Air Products) 10g / l

  Ink liquids Y-102 to 105 were prepared in the same manner as the ink liquid Y-101 except that the coloring matter was changed as shown in Table 2 below.

At this time, an ink liquid 101 was prepared using the comparative dye a in Table 2 as a comparative ink liquid.
Comparative dye a

  When changing the dye, it was used so that the added amount of the dye was equimolar with respect to the ink liquid Y-101.

  Further, a PM-G800 yellow ink cartridge manufactured by Epson Corporation was used as an ink comparison type.

  In Table 2, “ejection stability”, “light fastness”, “heat fastness”, “ozone resistance (gas) resistance”, “metal gloss”, “chromaticity”, and “solution stability” are Each ink is loaded into a yellow ink cartridge of an ink-jet printer PM-G800 manufactured by EPSON, the other color inks are inks of PM-G800, and the image receiving sheet is EPSON photographic paper <glossy> and EPSON photographic paper crispia < A yellow single-color image pattern and a green, red, and gray image pattern whose density changed stepwise to “high gloss” were printed, and image quality, ink ejection properties, and image fastness were evaluated.

  The following evaluation was performed on the inkjet inks of the above examples (ink liquids Y101, 102, 103, 104, 105) and the comparative example (ink liquid 201 and PM-G800 yellow ink). The results are shown in Table 2.

(Evaluation experiment)
1) About discharge stability, after setting a cartridge in a printer and confirming the protrusion of the ink from all the nozzles, 20 sheets of A4 were output and evaluated according to the following criteria.
A: No printing disturbance from the start to the end of printing B: Output with a printing disorder occurs C: There is a printing disturbance from the start to the end of printing

2) The image storability of the yellow dye was evaluated as follows using a print sample.
[1] Light fastness is measured by measuring the image density Ci immediately after printing with X-rite 310, and then irradiating the image with xenon light (100,000 lux) for 14 days using a weather meter manufactured by Atlas Co. Was measured to obtain a dye residual ratio Cf / Ci × 100. The afterimage rate of the dye is evaluated at three points of reflection density of 1, 1.5, and 2. A is the case where the dye residual rate is 80% or more at any concentration, and B is the case where the reflection point is less than 80%. When the concentration was less than 80%, C was designated.

[2] The heat fastness was evaluated by measuring the concentration of the sample before and after storage for 7 days under conditions of 80 ° C. and 60% RH with an X-rite 310 to determine the residual ratio of the dye. The afterimage rate of the dye is evaluated at three points of reflection densities of 1, 1.5, and 2. A is the case where the dye remaining rate is 95% or more at any concentration, and B is the case where the point is less than 95%. The case where the concentration was less than 95% was defined as C.

[3] For ozone resistance, the sample was left in a box where the ozone gas concentration was set to 5 ppm for 14 days, the image density before and after being left under ozone gas was measured using a reflection densitometer (X-Rite 310TR), As evaluated. The reflection density 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.
Evaluation was made in three stages, with A being a dye residual ratio of 80% or more at any concentration, A being 1 or 2 points being less than 80% B, and C being less than 70% at all concentrations.

3) Presence or absence of occurrence of metallic luster: The yellow, green and red solid print portions were visually observed and evaluated with reflected light.

4) Chromaticity: CIE L * a * b * was measured with SpectroEye manufactured by GretagMacbeth from a yellow monochromatic image pattern whose density changed stepwise. The following table shows a * b * with a reflection density of 1.0. Image receiving sheet is EPSON photo paper <Glossy>

5) Solution stability: A 10% by weight aqueous solution of the dye was aged for 10 days at 60 ° C. (pH≈8.0), and then the absorbance was measured. The change rate with respect to room temperature (23 ° C.) is shown in Table 2 below.

  From the results shown in Table 2, the system using the ink of the present invention has excellent ejection properties and weather resistance, suppresses the occurrence of metallic luster, and is excellent in hue as yellow (a * is minus = less reddish, b * Is large = color is high), and it was found that the solution stability was excellent.

  As is clear from the results in Table 2, it can be seen that the system using the ink of the present invention is excellent in all performance. In particular, the image fastness and the ink stability are superior to the comparative example.

  The same ink produced in Example 3 was printed on Fuji Photo Film inkjet paper photo glossy paper “Image” with the same machine of Example 3, and the same evaluation as in Example 3 was performed. Results were obtained.

(Preparation of ink liquid D)
2.5 g of the dye (DYE-19) of the present invention, 7.04 g of sodium dioctylsulfosuccinate, 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 Dissolve in 70 ml of ethyl acetate 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-grain dispersion is made into a microfluidizer (MICROFLUIDEX).
INC) to make fine particles by passing 5 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. This 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 liquid 103)
Ink liquid 103 was prepared in the same manner as ink liquid D, except that the dye of the present invention of 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 the same as those of the ink liquid D.

(Image recording and evaluation)
The ink liquid D and the comparative ink liquid 103 were evaluated as follows. The results are shown in Table 3 below.
In Table 3, the contents of “color tone (λmax)”, “light resistance”, “ozone resistance (gas)”, “heat resistance” and “ink stability” are the same as those described in Example 3. It is.

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

  When the same ink produced in Example 5 was printed on an inkjet paper photo glossy paper “Image Aya” manufactured by Fuji Photo Film using the same machine of Example 5, the same evaluation as in Example 5 was performed. Results similar to 5 were obtained.

  3 parts by mass of the dye (DYE-20) of the present invention and 100 parts by mass of a toner resin [styrene-acrylic acid ester copolymer; trade name Hymer TB-1000F (manufactured by Sanyo Kasei)] are mixed and ground by a ball mill, and then 150 ° C. Then, the mixture was melted and mixed, and after cooling, coarsely pulverized using a hammer mill, and then finely pulverized by 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, a sample was prepared in the same manner except that 3 parts by mass of the colorant shown in Table 4 was used. 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, O indicates that the hue is the best; Δ indicates that the hue is good, and X 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). The evaluation results are shown in Table 4 below. In Table 4 below, the case where the dye residual ratio is greater than 90% is indicated by ◯, the case where it is 90-80% is indicated by Δ, and the case where it is less than 80% is indicated by ×.

  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 transmittances greater than 80% were evaluated as ◯, 70-80% as Δ, and less than 70% as x. 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.

<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. A thermal transfer dye-donating material (5-1) was formed by coating so that the thickness at that time was 1.5 μm.

Thermal transfer dye-donating layer coating composition:
Dye (DYE-20) 10 mmol polyvinyl butyral resin (Denka Butyral 5000-A manufactured by Denki Kagaku) 3g
Toluene 40ml
Methyl ethyl ketone 40ml
Polyisocyanate (Takeda Takenate D110N) 0.2ml
Next, the thermal transfer dye-donating material of the present invention and the comparative thermal transfer dye-donating material (5-2) are prepared in the same manner as described above except that the dye (DYE-20) is changed to the comparative dye described in Table 5. did.

(Preparation of thermal transfer image receiving material) Using a synthetic paper (YUPO-FPG150 manufactured by Oji Oil Chemical Co., Ltd.) having a thickness of 150 μm as a support, the following composition is applied to the surface by wire bar coating so that the thickness when dried is 8 μm. Thus, a thermal transfer image receiving material was prepared. 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 (Dai Nippon Ink Chemical KP-90) 4g
Amino-modified silicone oil (KF-857 made by Shin-Etsu Silicone) 0.5g
85 ml of methyl ethyl ketone
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 is performed under the conditions of thermal head output of 0.25 W / dot, pulse width of 0.15 to 15 milliseconds, dot density of 6 dots / mm, and 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.

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>
3.4 parts by mass of cresol novolak resin (polystyrene equivalent weight average molecular weight 4300) obtained from a mixture of m-cresol / p-cresol / formaldehyde (reaction molar ratio = 5/5 / 7.5), phenol represented by the following formula O-naphthoquinonediazide-5-sulfonic acid ester produced using the compound (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 (DYE-20) 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 to light, it was heated at 100 ° C., and then the exposed area was removed by alkali development to obtain a positive colored pattern having a resolution of 0.8 μm. After the entire surface was exposed, it was 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, 2 parts 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>
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. ○ indicates good, Δ indicates an acceptable level, and × indicates an 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.

  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 (17)

The pigment | dye represented by the following general formula (I).
Formula (I)

In the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group. When n is 2, R, X, Y, Z, Q, and G each represent a monovalent or divalent substituent, and at least one represents a divalent substituent. When n is 3, R, X, Y, Z, Q, G represents a monovalent, divalent, or trivalent substituent, at least two represent a divalent substituent, or at least one is trivalent. Represents a substituent of However, when X represents a monovalent group, X represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. The dye according to claim 1, wherein one of the substituents on the heterocyclic group represented by G is -OM (M represents a hydrogen atom or a cation). The dye according to claim 1 or 2 , represented by the following general formula (1), general formula (2), general formula (3), general formula (4), or general formula (5).
General formula (1)

In the formula, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, and G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle M represents a hydrogen atom or a cation. m ₁ represents an integer of 0 to 3. However, X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.2 or more.
General formula (2)

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₁ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₂₁ and m ₂₂ each independently represent an integer of 0 to 3. However, X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.2 or more.
General formula (3)

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group, L ₂ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3. However, X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.2 or more.
General formula (4)

In the formula, R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₃ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3. However, X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.2 or more.
General formula (5)

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, and L ₄ is a divalent having a Hammett's σp value of 0.2 or more. Wherein G ₁ and G ₂ each independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3. X, X ₁ , X ₂ Each independently represents an electron-withdrawing group having a Hammett's σp value of 0.20 or more. X, X ₁ , X ₂ Are each independently an acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, aryl Sulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, The dye according to claim 1 or 2, wherein the dye represents a halogenated alkylthio group. In general formula (I), general formula (1), general formula (2), general formula (3), general formula (4), and general formula (5), nitrogen containing G, G ₁ and G ₂ The dye according to any one of claims 2 to 4, wherein the hetero ring is an S-triazine ring , a pyrimidine ring, a pyridazine ring, a pyrazine ring, or a pyridine ring . The dye according to claim 6, wherein one of the substituents on the nitrogen-containing heterocycle according to claim 6 is -OM (M represents a hydrogen atom or a cation). The dye according to any one of claims 2 to 7, wherein the dye represented by the general formula (1) is a dye represented by the following general formula (6).
General formula (6)

_{Wherein, R 1, R 2, Y} 1, and _{Y 2} represents a monovalent _{group, X 1,} X ₂ represents a σp value of 0.20 or more electron-withdrawing group with a Hammett's substituent constant independently. Z ₁ and Z ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted An aryl group, a substituted or unsubstituted heterocyclic group is shown. M represents a hydrogen atom or a cation. An ink containing at least one pigment according to any one of claims 1 to 8 . An ink for ink-jet recording using the ink according to claim 9 . An ink jet recording method for forming an image using the ink according to claim 10 . 11. An ink jet recording method comprising forming an image using an ink according to claim 10 on an image receiving material having an ink image receiving layer containing white inorganic pigment particles on a support. A method for improving the weather resistance of a colored image material formed using the ink according to claim 10 . An ink sheet containing at least one pigment according to any one of claims 1 to 8 . A color toner comprising at least one pigment according to any one of claims 1 to 8 . A color filter comprising at least one pigment according to any one of claims 1 to 8 . A compound represented by the following general formula (7), a salt or a hydrate thereof.
General formula (7)

(In the formula, R ₃ and R ₄ each independently represent a monovalent group, P ₁ and P ₂ each independently represent a hydrogen atom or a leaving group, and M represents a hydrogen atom or a cation.)