JP2006241217A - Phthalocyanine compound, coloring image-forming composition, and inkjet recording method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phthalocyanine compound having enough solubility in and fastness to a medium compatible with each other. <P>SOLUTION: This phthalocyanine compound is expressed by formula (1) (X<SB>1</SB>to X<SB>4</SB>are each -SO-Z, -SO<SB>2</SB>-Z, -SO<SB>2</SB>NR<SB>1</SB>R<SB>2</SB>, sulfo, -CONR<SB>1</SB>R<SB>2</SB>, -CO<SB>2</SB>R<SB>1</SB>or -COR<SB>1</SB>). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel phthalocyanine compound, a colored image forming composition containing the same, and an ink jet recording method using the same.

  Various color materials (dyes and pigments) used for inkjet recording materials, thermal transfer recording materials, electrophotographic recording materials, printing inks, recording pens, displays and color filters for CCDs have been developed so far. However, the fact is that there are no robust dyes that can withstand various use conditions and environmental conditions, and improvements are strongly desired.

  The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.

  The pigment used in such an ink jet ink has good solubility or dispersibility in a solvent, is capable of high-density recording, is excellent in ink storage stability, has a good hue, light, Fast against heat and environmental active gases (NOx, ozone, and other oxidizing gases, SOx, etc.), excellent fastness to water and chemicals, good fixability to image receiving materials It is required that the ink does not bleed easily, has excellent long-term storage stability as an ink, has no toxicity, has high purity, and can be obtained at low cost.

  Until now, phthalocyanine compounds have been used as cyan dyes used in ink jet inks in most cases. These often lack solubility due to dye association, while in the case of structures with enhanced solubility, they do not have sufficient fastness to light and oxidizing gases (especially ozone) This solution was desired.

  In addition, the water-based ink mainly used as an ink for ink jet recording (hereinafter also referred to as “ink jet recording ink”) has a large water resistance such that a recorded image is blurred or disappears with water. There was a problem.

As a technique for solving this problem, an ink using a pigment or an oil-soluble dye as a coloring matter, a method of adding an organic solvent, a resin, or the like to an aqueous ink using a water-soluble dye have been studied. More recently, inks using aqueous dispersions in which a polymer colored with a dye or pigment is used as a dispersoid have been described (see, for example, Patent Documents 1 to 3).
In addition, ultraviolet curable inks using a polyfunctional monomer having excellent adhesion to a recording material are disclosed as being suitable for printing on a non-water-absorbing recording material while improving water resistance (for example, And Patent Documents 4 and 5).

However, if a pigment dispersion is used as a coloring component in these methods, the nozzles may become clogged due to aggregation of the pigment, making it difficult to stably eject ink, and insufficient transparency and color tone. Therefore, development of an ink using a dye has been desired.
However, even when a phthalocyanine compound soluble in an organic solvent is used as an ink jet recording dye, there is a problem that the ink has a low solubility in a medium as described above, and an ink having a required concentration cannot be produced. In the case of a highly soluble phthalocyanine compound, there has been a problem that the image is discolored or fading easily due to long-term light exposure or an active gas (SOx, NOx, ozone, etc.) in the environment.
As a technique for solving these problems, a method for imparting solubility of a phthalocyanine dye by introducing a substituent that imparts solubility to the mother nucleus of the phthalocyanine dye is disclosed (for example, see Patent Document 6). ).
However, the solubility, light resistance, ozone resistance and the like are not always sufficient.

Thus, when the phthalocyanine compound used as a cyan dye is used as an oil-soluble dye, it has been strongly demanded to develop a compound having both good solubility in an ink medium and good light resistance and ozone resistance.
JP-A-6-340835 International Publication No. 00/08102 Pamphlet JP 2004-231882 A JP-T-2001-512777 (pages 1 to 3, pages 11 to 15) JP-A-5-214279 (first page, fourth to fifth page) Japanese Patent Laid-Open No. 2003-12956

An object of the present invention is to provide a phthalocyanine compound, particularly a cyan dye, as a colorant having both sufficient solubility in a medium and fastness.
Another object of the present invention is to provide a novel colored image forming composition having light fastness and sufficient fastness (ozone resistance) against active gases in the environment using the phthalocyanine compound. .
Still another object of the present invention is to provide an ink jet method using the colored image forming composition.

In view of the above circumstances, the present inventors have conducted extensive research and have solved the above problems by using a compound represented by the following general formula (1) in which a specific substituent is introduced into a novel phthalocyanine compound. As a result, the present invention was completed.
That is, the present invention is achieved by the following means.

<1> A phthalocyanine compound represented by the following general formula (1).

[In the general formula (1), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , —CONR ₁ R ₂ , —CO ₂ represents R ₁ or —COR ₁ . Z independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₁ and R ₂ are each independently 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 aryl group, substituted or unsubstituted Represents a heterocyclic group.
One or more groups of Z, R ₁ and R ₂ include —CO ₂ — (CR ₃ R ₄ ) n—CO ₂ R ₅ — as a substituent. Here, R ₃ and R ₄ each independently represents a substituted or unsubstituted alkyl group or a hydrogen atom, R ₅ represents an alkyl group, n represents an integer of 1 to 20, and n is an integer of 2 or more. Sometimes a plurality of R ₃ and R ₄ may be the same or different.
Y _{1 to} Y ₄ each independently represent a hydrogen atom or a monovalent substituent. _{a 1 ~a 4, b 1 ~b} 4 are each X ₁ to X _4, and represents the number of substituents Y ₁ to Y _4. a _{1 to} a ₄ each independently represents a number from 0 to 4, but they are not all 0 at the same time. b ₁ ~b ₄ represents the number of independently 0-4. When a _{1 to} a ₄ and b _{1 to} b ₄ represent a number of 2 or more, the plurality of X _{1 to} X ₄ and Y _{1 to} Y ₄ may be the same or different. M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. ]

<2> The phthalocyanine compound according to <1>, wherein the general formula (1) is represented by the following general formula (2).

［一般式（２）中、Ｘ₁〜Ｘ₄、Ｍは前記一般式（１）中のＸ₁〜Ｘ₄、Ｍとそれぞれ同義である。ａ₁〜ａ₄はそれぞれ独立に１又は２の整数を表す。］

[In the general formula _{(2), X 1 ~X 4} , M are respectively the X ₁ to X _4, M in the general formula (1) in the same meaning. a _{1 to} a ₄ each independently represents an integer of 1 or 2. ]

<3> A colored image forming composition comprising the phthalocyanine compound according to <1> or <2>.

<4> The colored image forming composition as described in any one of <1> to <3> above, which is used for inkjet recording.

<5> An ink jet recording method comprising forming an image using the colored image forming composition according to the above <4>.

According to the present invention, it is possible to provide a phthalocyanine compound, particularly a cyan dye, as a colorant having both sufficient solubility in a medium and fastness.
Further, according to the present invention, it is possible to provide a novel colored image forming composition having light fastness and sufficient fastness (ozone resistance) against active gases in the environment using the phthalocyanine compound. .
Furthermore, according to the present invention, it is possible to provide a colored image forming composition (ink jet ink) used for ink jet recording having light resistance and sufficient fastness (ozone resistance) against an active gas in the environment. .
Furthermore, according to the present invention, an ink jet method using the colored image forming composition can be provided.

The novel phthalocyanine compound represented by the following general formula (1) of the present invention will be described in detail.
≪Phthalocyanine compound≫

In the general formula (1), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , —CONR ₁ R ₂ , —CO _2. R ₁ or —COR ₁ is represented. Z independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₁ and R ₂ are each independently 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 aryl group, substituted or unsubstituted Represents a heterocyclic group.
One or more groups of Z, R ₁ and R ₂ include —CO ₂ — (CR ₃ R ₄ ) n—CO ₂ R ₅ — as a substituent. Here, R ₃ and R ₄ each independently represents a substituted or unsubstituted alkyl group or a hydrogen atom, R ₅ represents an alkyl group, n represents an integer of 1 to 20, and n is an integer of 2 or more. Sometimes a plurality of R ₃ and R ₄ may be the same or different.
Y _{1 to} Y ₄ each independently represent a hydrogen atom or a monovalent substituent. _{a 1 ~a 4, b 1 ~b} 4 are each X ₁ to X _4, and represents the number of substituents Y ₁ to Y _4. a _{1 to} a ₄ each independently represents a number from 0 to 4, but they are not all 0 at the same time. b ₁ ~b ₄ represents the number of independently 0-4. When a _{1 to} a ₄ and b _{1 to} b ₄ represent a number of 2 or more, the plurality of X _{1 to} X ₄ and Y _{1 to} Y ₄ may be the same or different. M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof.

In the general formula (1), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , —CONR ₁ R ₂ , —CO _2. R ₁ or —COR ₁ is represented.
It is preferable to have at least one of these substituents on each benzene ring of the phthalocyanine mother nucleus. Among these substituents, —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , or —CONR ₁ R ₂ are preferable, and —SO ₂ —Z or —SO ₂ NR ₁ R _{2 is} particularly preferable. Is most preferred.
Here, as described above, when a _{1 to} a ₄ representing the number of substituents represent a number of 2 or more, the plurality of X _{1 to} X ₄ may be the same or different from each other, and Represents the group.

  Z independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Preferred are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. Among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are most preferred.

R ₁ and R ₂ are each independently 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 aralkyl group, substituted or unsubstituted Represents an aryl group or a substituted or unsubstituted heterocyclic group. Preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferred. Most preferred.

The substituted or unsubstituted alkyl group represented by R ₁ , R ₂ and Z is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 5 to 25, and particularly preferably 5 to 20. In particular, a branched alkyl group is preferred because it increases the solubility of the dye and the ink stability.
Examples of the substituent include the same substituents as those described later when Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ , and Y ₄ can further have a substituent. Of these, a hydroxyl group, an ether group, an ester group, an amide group, a sulfonamide group, and a phenyl group are particularly preferable. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted cycloalkyl group R _1, R ₂ and Z represents the total number of carbon atoms is preferably a cycloalkyl group having 3 to 30, more preferably from 5 to 25, particularly preferably from 5 to 15. In particular, the case of having an asymmetric carbon (use in a racemic form) is particularly preferred because of increasing the solubility of the dye and the ink stability.
Examples of the substituent include the same substituents as those described later when Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ , and Y ₄ can further have a substituent. Of these, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, a sulfonamide group, and a phenyl group are particularly preferable. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted alkenyl group R _1, R ₂ and Z represents the total number of carbon atoms is preferably an alkenyl group having 2 to 30, more preferably 2 to 20, particularly preferably from 4 to 15. In particular, a branched alkenyl group is preferred because it increases the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in a racemic form).
Examples of the substituent include the same substituents as those described later when Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ , and Y ₄ can further have a substituent. Of these, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, a sulfonamide group, and a phenyl group are particularly preferable. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted aryl group represented by R _1, R ₂ and Z, the total number of carbon atoms is an aryl group having from 6 to 30, more preferably 10 to 25, particularly preferably 15 to 25.
Examples of the substituent include the same substituents as those described later when Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ , and Y ₄ can further have a substituent. Among them, halogen atom, heterocyclic group, cyano group, carboxyl group, acylamino group, sulfonamido group, sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfo group, quaternary ammonium group are preferable, cyano group, carboxyl Group, sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfo group, and quaternary ammonium group are more preferable.

The substituted or unsubstituted heterocyclic group represented by R ₁ , R ₂ and Z is preferably a 5-membered or 6-membered ring, which may be further condensed. Further, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. Examples of the heterocyclic group represented by R ₁ , R ₂ and Z are shown below in the form of a heterocyclic ring in which the substitution position is omitted, but the substitution position is not limited. Substitutions at the 3rd and 4th positions are possible. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole Benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Among them, an aromatic heterocyclic group is preferable, and preferable examples thereof are the same as those described above. And thiadiazole.
Examples of the substituent include the same substituents as those described later when Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ , and Y ₄ can further have a substituent. . Preferred substituents are the same as those of the aryl group, and more preferred substituents are the same as the more preferred substituent of the aryl group.

Y ₁ , Y ₂ , Y ₃ , and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include a halogen atom, an alkyl group, a cycloalkyl group, and an alkenyl group. , Aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, acylamino group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, Arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxy Carbonylamino group, imide group, heterocyclic thio group, Digging group, an acyl group, a carboxyl group, or sulfo group, each of which may further have a substituent.
Y ₁ , Y ₂ , Y ₃ , and Y ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, or a sulfonamide group. , A carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, or a sulfo group, particularly preferably a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, or a sulfo group.

When Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ are groups that can further have a substituent, they may further have a substituent as listed below. .
Examples of the substituent for Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ include a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched chain having 2 to 12 carbon atoms. Chain alkenyl group, linear or branched alkynyl group having 2 to 12 carbon atoms, linear or branched cycloalkyl group having 3 to 12 carbon atoms, linear or branched cycloalkenyl group having 3 to 12 carbon atoms (more Each group preferably has a branched chain because it improves the solubility of the dye and the stability of the ink. For example, methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonyl Ethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (eg, chlorine atom, bromine atom), aryl group (eg, phenyl, 4-t-butylphenyl, 2,4 -Di-t-amylphenyl), a heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, An amino group, an alkyloxy group (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), an aryloxy group (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino groups (for example, acetamide, benzamide, 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide), alkylamino groups (for example, methylamino, Butylamino, di Tilamino, methylbutylamino), anilino group (for example, phenylamino, 2-chloroanilino, ureido group (for example, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (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), alkyl Oxycarbonylamino group (for example, methoxycarbonylamino), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N- Butylcarbamoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl) , Alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxy) Phenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenyl) Carbamoyloxy), silyloxy groups (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino groups (for example, phenoxycarbonylamino), imide groups (for example, N-succinimide, N-phthalimide), heterocyclic thio groups ( For example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, , Phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), acyl groups (eg acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (eg Carboxyl group, a sulfo group, a phosphono group and a quaternary ammonium group).

In the general formula (1), at least one of Z, R ₁ and R ₂ includes —CO ₂ — (CR ₃ R ₄ ) n—CO ₂ R ₅ — as a substituent. Here, R ₃ and R ₄ each independently represents a substituted or unsubstituted alkyl group or a hydrogen atom.
The alkyl group represented by R ₃ and R ₄ may be either unsubstituted or substituted alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 10, and particularly preferably 1 to 5.
The alkyl group represented by R ₅ may be either unsubstituted or substituted alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 10 and particularly preferably 1 to 5.
n represents an integer of 1 to 20, preferably 1 to 10, and particularly preferably 1 to 5. When n is an integer of 2 or more, the plurality of R ₃ and R ₄ may be the same as or different from each other.

The _{-CO 2 - (CR 3 R 4} ) n-CO 2 R 5 - The position structures may introduce represented by a X ₁ to X _4, Y ₁ to Y _4, is the number 1 or 16 It is in the following range, preferably 3 or more and 5 or less, more preferably 4. Moreover, as the introduction position of this structure, positions represented by X _{1 to} X ₄ are preferable.

Wherein _{a 1 ~a 4, b 1 ~b} 4 are each X ₁ to X _4, and represents the number of substituents Y ₁ to Y _4. a _{1 to} a ₄ each independently represents a number from 0 to 4, but they are not all 0 at the same time. b ₁ ~b ₄ represents the number of independently 0-4. When a _{1 to} a ₄ and b _{1 to} b ₄ represent a number of 2 or more, the plurality of X _{1 to} X ₄ and Y _{1 to} Y ₄ may be the same or different.
a ₁ and b ₁ each represents an independent number of 0 to 4 satisfying the relationship of a ₁ + b ₁ = 4, and particularly preferably, the combination of a ₁ and b ₁ is 1 and 3, or 2 and 2 a combination that represents a combination of a1 and b ₁ among them is most preferably 1 and 3.
Each combination of (a ₂ , b ₂ ), (a ₃ , b ₃ ), (a ₄ , b ₄ ) has the same relationship as a ₁ , b ₁ , and the preferred combination is also the same.

M represents a hydrogen atom, a metal atom, or an oxide, hydroxide or halide thereof. Preferably, M is a hydrogen atom, and a metal atom is Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd , Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like. VO and GeO as oxides, Si (OH) ₂ , Cr (OH) ₂ and Sn (OH) ₂ as hydroxides, AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl as halides , FeCl, GaCl, ZrCl and the like, among which Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable.

  The general formula (1) is preferably a compound represented by the following general formula (2).

In the general formula (2), X ₁ to X _4, M are each a X ₁ to X _4, M in said general formula (1) synonymous, are the preferable examples. a _{1 to} a ₄ each independently represents an integer of 1 or 2.

  Hereinafter, although the specific example of the compound of this invention is shown, the compound of this invention is not restricted to these.

  The phthalocyanine compound represented by the general formula (1) of the present invention can be synthesized with reference to JP-A No. 2003-213168.

In general, when a phthalocyanine compound is represented as a phthalocyanine compound represented by the following general formula (IV), the derivative is inevitably substituted at the position of substitution Rn (n = 1 to 16) (R ₁ : 1 position to R ₁₆ may include isomers (defined herein as position 16), and these substitutional isomers are often regarded as the same derivative without being distinguished from each other. Further, even when isomers are included in the substituent of R, they are often regarded as the same phthalocyanine derivative without distinction.

  The case where the structures of the phthalocyanine compounds defined in this specification are different from each other will be described in the general formula (IV). When the constituent atomic species of the substituent Rn (n = 1 to 16) are different, the number of the substituent Rn is Either it is different or the position of the substituent Rn is different.

The phthalocyanine derivative represented by the general formula (1) inevitably has different introduction positions and numbers of substituents Xn (n = 1 to 4) and Ym (m = 1 to 4) depending on the synthesis method. In general, the mixture is a mixture, and the analog mixture is often represented by a statistical average.
These phthalocyanine dye analog mixtures are classified and defined into the following three types based on the substitution position of the general formula (IV).

  (1) β-position substitution type: phthalocyanine dye having a specific substituent at the 2 and / or 3 position, the 6 and / or 7 position, the 10 and / or 11 position, the 14 and / or 15 position.

  (2) α-position substitution type: phthalocyanine dye having a specific substituent at 1 and / or 4 position, 5 and / or 8 position, 9 and / or 12 position, 13 and / or 16 position.

  (3) α, β-position mixed substitution type: phthalocyanine dye having a specific substituent without regularity at positions 1 to 16.

  In the present specification, when describing derivatives of phthalocyanine compounds having different structures (particularly, different substitution positions), the β-position substitution type, α-position substitution type, and α, β-position mixed substitution type are used. .

  The phthalocyanine compound of the present invention can be obtained by, for example, Shirai-Kobayashi, published by IPC Co., Ltd. “Phthalocyanine—Chemistry and Function” (P. 1-62), C.I. C. Leznoff-A. B. P. Lever co-authored, published by VCH, described in 'Phthalocyanines-Properties and Applications' (P. 1-54), etc., can be synthesized by combining quoted or similar methods.

  The phthalocyanine compound represented by the general formula (1) of the present invention is disclosed in pamphlets of International Publication Nos. 00/17275, 00/08103, 00/08101, and 98/41853, and JP-A-10-36471. For example, it can be synthesized through sulfonation, sulfonyl chlorideation, and amidation reaction of an unsubstituted phthalocyanine compound. In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonation is difficult to control. Therefore, when a sulfo group is introduced under such reaction conditions, the position and number of the sulfo group introduced into the product cannot be specified, and a mixture in which the number of substituents and the substitution position are different is always given. Therefore, when synthesizing the compound of the present invention using it as a raw material, the number and substitution position of the heterocyclic substituted sulfamoyl group cannot be specified, so the compound of the present invention includes several types of compounds having different numbers of substituents and substitution positions. Α, β-position mixed substitution mixture.

  As described above, for example, when a large number of electron withdrawing groups such as sulfamoyl groups are introduced into the phthalocyanine nucleus, the oxidation potential becomes more noble and the ozone resistance is enhanced. According to the above synthesis method, it is inevitable that a small amount of electron-withdrawing groups are introduced, that is, a phthalocyanine dye having a lower oxidation potential is mixed. Therefore, in order to improve ozone resistance, it is more preferable to use a synthesis method that suppresses the formation of a compound having a lower oxidation potential.

  The phthalocyanine compound represented by the general formula (2) of the present invention is, for example, a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following formula represented by the general formula (V). Derived from a tetrasulfophthalocyanine compound obtained by reacting a 4-sulfophthalonitrile derivative (compound R) represented by the following formula with a metal derivative represented by the general formula (V): can do.

In the above formulas, Xp corresponds to X _{1 to} X ₄ (when a1 to a4 = 1) in the general formula (2). Yq and Yq ′ represent a hydrogen atom. In Compound R, M ′ represents a cation.

In the general formula (V) (M- (Y) d), M is the same as M in the general formulas (1) and (2), and Y is a halogen atom, acetate anion, acetylacetonate, oxygen, or the like. A monovalent or divalent ligand is shown, and d is an integer of 1 to 4.
Examples of the metal derivative represented by the general formula (V) include halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides and complexes of the metal atom of the general formula (1).
Specific examples include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, zinc iodide, acetic acid. Examples include zinc, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride and the like.

  The amount of the phthalonitrile compound represented by the general formula (V) metal derivative and the compound P is preferably 1: 3 to 1: 6 in molar ratio. The amount of the diiminoindoline derivative represented by the general formula (V) metal derivative and the compound Q is preferably 1: 3 to 1: 6 in molar ratio.

  The reaction is usually performed in the presence of a solvent. As the solvent, an organic solvent having a boiling point of 80 ° C. or higher, preferably 130 ° C. or higher is used. For example, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, Examples include triethylene glycol, polyethylene glycol, 1-methoxy-2-propanol, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylaminoethanol, diethylaminoethanol, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, and urea. The usage-amount of a solvent is 1-100 mass times of a phthalonitrile compound, Preferably it is 5-20 mass times.

  In the reaction, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or ammonium molybdate may be added as a catalyst. The addition amount is 0.01 to 10 times mol, preferably 0.01 to 2 times mol for 1 mol of the phthalonitrile compound and / or diiminoisoindoline derivative.

  The reaction temperature is preferably 70 to 300 ° C., preferably 70 to 250 ° C., more preferably 70 to 190 ° C. Below 60 ° C, the reaction rate is extremely slow. If it exceeds 300 ° C, the phthalocyanine compound may be decomposed.

  The reaction time is preferably 0.5 to 20 hours, preferably 0.5 to 15 hours, and particularly preferably 0.5 to 10 hours. If it is less than 0.5 hour, there are many unreacted raw materials, and if it is 20 hours or more, the phthalocyanine compound may be decomposed.

  The product obtained by these reactions is processed according to a post-treatment method of a normal organic synthesis reaction, and then used as a product with or without purification. That is, for example, the product liberated from the reaction system can be provided as a product by performing the operation of purification by recrystallization or column chromatography alone or in combination without purification. Further, after completion of the reaction, the reaction solvent is distilled off, or it is poured into water, ice, or an organic solvent without being distilled off, and it is neutralized or purified without being neutralized, without purification. Alternatively, the product can be provided as a product after performing an operation of purification by recrystallization, column chromatography or the like alone or in combination. After completion of the reaction, the reaction solvent is distilled off or poured into water, ice, or an organic solvent without being distilled off, and is extracted with an organic solvent / aqueous solution with or without neutralization. The product can be provided as a product after purification or purification by crystallization or column chromatography, either alone or in combination.

  According to the above synthesis method, a specific number of desired substituents can be introduced. In particular, when a large number of electron withdrawing groups are to be introduced in order to make the oxidation potential noble as in the present invention, the above synthesis method is extremely excellent as the synthesis method of the general formula (2).

  The obtained compound represented by the general formula (2) is usually a mixture of compounds represented by the following general formulas (a) -1 to (a) -4, which are isomers at each substitution position of Xp, β-position substitution type.

  The compounds represented by the above general formulas (a) -1 to (a) -4 are β-position substituted (2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and And / or a phthalocyanine compound having a specific substituent at the 15-position), which has a completely different structure from the α-position substituted type and the α, β-position mixed substituted type (the position at which the specific substituent is introduced is different). is there.

  The required properties for the colored image-forming composition described below are (1) appropriate physical properties such as viscosity, surface tension, specific conductivity, density, pH, and (2) high dissolution stability of the dissolved components, (3) Good quick-drying on the recording material, (4) Clear recorded image, good light resistance and water resistance, (5) Good long-term storage stability, Etc. In addition, in the case of inkjet recording, in addition to the above, the nozzle may not be clogged in (2).

  In addition, the colored image forming composition in the ink cartridge has a large problem that the coloring compound is prepared at a high concentration, so that the coloring compound is deposited by long-term storage and exposure to high and low temperatures. .

  To date, various studies have been made focusing on the above-mentioned (1) to (5) and the like, but conventional colored image forming compositions have not yet satisfied all these characteristics.

  The colored image forming composition of the present invention satisfies the above required characteristics (1) to (5), and in particular, in order to achieve the object of the present invention, a phthalocyanine compound having a specific substituent introduced into the phthalocyanine mother nucleus. contains.

  Conventionally, in order to satisfy various fastnesses (light, ozone gas, etc.) and hue, one of the solutions has been to promote association of phthalocyanine compounds. However, not only phthalocyanine compounds but all organic substances have a tendency that the aggregates of molecules become huge and eventually crystallize as association grows.

  Conventional phthalocyanine compounds often lack solubility due to dye association. In general, when water-soluble or oil-soluble phthalocyanine is present in a solvent without each molecule being associated, many solvent molecules are present so as to surround the molecule. That is, the phthalocyanine molecule is solvated by the solvent molecules, and the molecules are dissolved. However, when the phthalocyanine compound interacts (associates) with each other and begins to aggregate, it becomes difficult to undergo solvation of the solvent and eventually becomes insoluble.

  That is, if the molecular aggregates are controlled so as not to become large, it is possible to prevent molecular precipitation. As a result of intensive studies for this purpose, the introduction of two ester groups linked by a carbon chain significantly improves the affinity between the solvent and phthalocyanine and improves the solubility, while also improving various fastness properties. The present inventors have found that the contributing molecular association is sufficiently retained, and have reached the present invention.

That is, the phthalocyanine compound of the present invention which satisfies both required properties and suppression of crystallization for dyes used in the colored image-forming composition described later, the X ₁ to X _4, Y ₁ to Y ₄ in the general formula (1) 2 It has been found that by introducing a specific substituent having one or more ester structures, not only the affinity and solubility to a solvent are remarkably improved, but also light resistance and ozone resistance are extremely excellent.

Examples of the use of the phthalocyanine compound of the present invention include image recording materials for forming images, particularly color images, and specifically, thermal transfer type images including inkjet recording materials described in detail below. Recording materials, pressure-sensitive recording materials, recording materials using electrophotographic methods, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink-jet recording materials, thermal transfer type image recording materials, electrophotographic methods In particular, an ink jet recording material is preferable.
Also applicable to color filters used in solid-state imaging devices such as LCDs and CCDs described in US Pat. No. 4,808,501 and JP-A-6-35182, and dyeing solutions for dyeing various fibers. it can.
The coloring matter of the phthalocyanine compound of the present invention is used by adjusting the physical properties such as solubility and heat transfer property suitable for the use by a substituent. The phthalocyanine compound can be used in a uniform dissolved state, a dispersed dissolved state such as an emulsified dispersion, or a solid dispersed state depending on the system used.

≪Colored image forming composition≫
<Colored image forming composition>
The colored image forming composition of the present invention contains the phthalocyanine compound of the general formula (1) as a colorant, and other colorants can be used.
The colored image forming composition of the present invention contains the phthalocyanine compound represented by the general formula (1), thereby having light fastness and ozone resistance having sufficient fastness to light, heat, humidity, and active gas in the environment. It can be set as the colored image forming composition excellent in property.

  The phthalocyanine compound of the present invention contained in the colored image forming composition of the present invention acts as a colorant for recording materials and the like, but is preferably used as a phthalocyanine dye, and more preferably used as a cyan dye. .

  The colored image forming composition of the present invention is suitably used as an ink composition for ink jet recording (hereinafter also referred to as “ink jet ink”).

  The colored image forming composition of the present invention can contain other additives described below, as long as the effects of the present invention are not impaired.

  Examples of the other additives include drying inhibitors (wetting agents), penetration enhancers, UV absorbers, antifading agents, antifungal agents, pH adjusters, surface tension adjusters, antifoaming agents, and emulsion stabilizers. , Known additives such as preservatives, viscosity modifiers, dispersants, dispersion stabilizers, rust inhibitors and chelating agents.

(Other additives)
The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink-jet ink at the ink jet port of the nozzle used in the ink-jet recording method.

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

  The penetration accelerator is preferably used for the purpose of allowing the ink to penetrate better into the paper. As penetration enhancers, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants, etc. can be used. . These are preferably contained in the colored image forming composition in an amount of 3 to 30% by mass, and preferably 5 to 30% by mass when used for inkjet applications. These amounts usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  The ultraviolet absorber is used for the purpose of improving image storability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, U.S. Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-21114, Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-A-8 No. -502911, etc., triazine compounds, Research Disclosure No. The compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based compounds and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

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

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

  As the pH adjuster, the neutralizing agent (organic base, inorganic alkali) can be used. In order to improve the storage stability of the ink for ink jet recording, the pH adjuster is preferably added so that the ink for ink jet recording has a pH of 6 to 10, and is preferably added to have a pH of 7 to 10. More preferred.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

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

<Method for adjusting colored image forming composition>
The method for preparing the colored image forming composition of the present invention is not particularly limited, and any method can be used. However, as a water-based composition in which the phthalocyanine compound in the present invention is dispersed in an aqueous medium, or a polymerizable group. It is preferable to obtain it as an active energy curable composition (hereinafter also referred to as “curable composition”) obtained by dispersing it in the monomer it has.

[Aqueous composition]
When the phthalocyanine compound of the present invention is dispersed in an aqueous medium, as described in JP 2001-240763 A, JP 2001-262039 A, JP 2001-247788 A, and the like, a dye and an oil-soluble polymer are used. Or the compound of the present invention dissolved in a high-boiling organic solvent as described in JP-A Nos. 2001-240763 and 2001-335734 in an aqueous medium. It is preferable to disperse.

-Specific method of dispersion-
The specific method for dispersing the compound of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the above-mentioned patent publications, etc. can do. Alternatively, the phthalocyanine compound 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 preparation method of the aqueous composition in the colored image forming composition, besides the above-mentioned patents, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, 7- Details are described in Japanese Patent Nos. 118584, 11-286637, and 2000-203856, and can also be used for the preparation of the colored image forming composition of the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.

[Curable composition]
The phthalocyanine compound of the present invention is also preferably used in a curable composition (active energy curable, colored image forming composition), and is also referred to as an active energy curable inkjet ink (hereinafter also referred to as “curable inkjet ink”). It is also preferable to use for the above.
This active energy curable colored image forming composition (hereinafter also referred to as “curable composition”) is a monomer having a polymerizable group and an oil-soluble dye having a specific structure. A colored image-forming composition containing any other compound, and may contain other components appropriately selected as necessary.
As other components, the above-mentioned other additives, such as anti-drying agents, penetration enhancers, antioxidants, antifungal agents, pH regulators, surface tension regulators, antifoaming agents, viscosity modifiers, dispersants, dispersions Well-known additives, such as a stabilizer, a rust preventive agent, a chelating agent, are mentioned.

As the active energy ray for proceeding the polymerization of the monomer, α ray, γ ray, X ray, ultraviolet ray, visible ray, electron beam and the like can be used. Of these, ultraviolet rays and visible rays are preferably used from the viewpoint of cost and safety, and ultraviolet rays are more preferably used.
When ultraviolet rays, visible rays, etc. are used as active energy rays, a photopolymerization initiator for initiating polymerization is used in combination.
Therefore, the said curable composition concerning the other structure of this invention contains the photoinitiator for starting superposition | polymerization of monomers.
That is, the active energy curable inkjet ink containing the compound of the present invention includes a cationic polymerizable group, a radical polymerizable group, an anion polymerizable group, preferably a monomer having a cationic polymerizable group or a radical polymerizable group, light Polymerization initiators, sensitizers, and other additives can be used.

-Monomer having a polymerizable group-
As the monomer having a polymerizable group used in the present invention, a compound having a polymerizable double bond (polymerizable group) that is solidified by application of the active energy ray (for example, energy such as ultraviolet ray, heat, or electron beam). It is. Monomers are required to use bifunctional or higher functional compounds (hereinafter referred to as “polyfunctional monomers”), and are monofunctional for viscosity adjustment, crosslinking density adjustment, and physical property control (strength, adhesion, etc.) after curing. These compounds (hereinafter referred to as “monofunctional monomers”) may be used in combination.

  Examples of the polymerizable group include an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, and an internal double bond group (such as maleic acid). Among them, an acryloyl group and a methacryloyl group can be cured with low energy. Preferably, an acryloyl group is particularly preferable.

  The polyfunctional monomer is a vinyl group-containing aromatic compound, an acrylate which is an ester of a divalent or higher alcohol and acrylic acid or methacrylic acid, or an amide of a divalent or higher amine and acrylic acid or methacrylic acid. Acrylamide, polyester obtained by combining acrylic acid or methacrylic acid with polycaprolactone or ester obtained by combining polybasic acid and dihydric alcohol, or ether obtained by combining alkylene oxide and polyhydric alcohol with acrylic acid or methacrylic acid Polyether acrylate introduced with epoxy, epoxy acrylate obtained by introducing acrylic acid or methacrylic acid into an epoxy resin, or reacting a dihydric or higher alcohol with an epoxy-containing monomer, urethane acrylate having a urethane bond Rate, amino resin acrylate, acrylic resin acrylate, alkyd resin acrylate, spirane resin acrylate, silicone resin acrylate, reaction product of unsaturated polyester and photopolymerizable monomer, and reaction product of waxes and polymerizable monomer Acrylates, polyester acrylates, polyether acrylates, epoxy acrylates, urethane acrylates, acrylic resin acrylates, silicone resin acrylates, reaction products of unsaturated polyesters and the above photopolymerizable monomers are preferred, acrylates, polyester acrylates, polyether acrylates, Epoxy acrylate and urethane acrylate are particularly preferable.

  Examples of the polyfunctional monomer include divinylbenzene, 1,3-butanediol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, 1,6 -Acryloylaminohexane, hydroxypivalate ester neopentyl glycol diacrylate, polyester acrylate having a (meth) acryloyl group at the molecular chain end of a polyester having a molecular weight of 500 to 30,000 comprising a dibasic acid and a dihydric alcohol, polyethylene glycol diacrylate, Molecule containing bisphenol (A or S, F) skeleton containing skeleton of epoxy acrylate having a molecular weight of 450 to 30,000 and phenol novolac resin Epoxy acrylates of from 600 to 30,000, the reaction product of a polyvalent isocyanate and a hydroxyl group (meth) acrylate monomer having a molecular weight of 350 to 30,000, also urethane-modified product having a urethane bond in the molecule.

  Examples of the monofunctional monomer include substituted or unsubstituted (meth) acrylate, substituted or unsubstituted styrene, substituted or unsubstituted acrylamide, vinyl group-containing monomers (vinyl esters, vinyl ethers, N-vinylamide, etc.), (Meth) acrylic acid, etc., and substituted or unsubstituted (meth) acrylate, substituted or unsubstituted acrylamide, vinyl esters and vinyl ethers are preferred, substituted or unsubstituted (meth) acrylate, substituted or unsubstituted Acrylamide is particularly preferred.

  Examples of the monofunctional monomer include hydroxyethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, 2-acryloyloxyethyl phosphate, allyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethyl. Acrylamide, N, N-diethylaminopropylacrylamide, N-butoxymethylacrylamide, acryloylmorpholine, 2-hydroxyethyl vinyl ether, N-vinylformamide, N-vinylacetamide, 2-cyclohexylcarbamoyloxyethyl acrylate, polybutylacrylate moiety on ester Acrylate containing, acrylate containing polydimethylsiloxane moiety in ester, etc. .

The content of the monomer in the curable composition is usually preferably in the range of 50 to 99.6% by mass, more preferably 70 to 99.0% by mass, and even more preferably 80 to 99.0% by mass.
The monomer may be any monomer as long as the effect of the present invention can be obtained, but is more preferably selected from those having high safety.
Monomers having high safety are those having a small value of PII (skin irritation), PII is preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.0 or less, and 5 or less is particularly preferable.

-Photopolymerization initiator and sensitizer-
The photopolymerization initiator is not particularly limited as long as radicals generated by light and other active species react with the polymerizable double bond in the monomer.
As photopolymerization initiators, acetophenone derivatives, benzophenone derivatives, benzyl derivatives, benzoin derivatives, benzoin ether derivatives, benzyl dialkyl ketal derivatives, thioxanthone derivatives, acylphosphine oxide derivatives, metal complexes, p-dialkylaminobenzoic acids, azo compounds, Peroxide compounds are generally known, and acetophenone derivatives, benzyl derivatives, benzoin ether derivatives, benzyl dialkyl ketal derivatives, thioxanthone derivatives, and acyl phosphine oxide derivatives are preferred, and acetophenone derivatives, benzoin ether derivatives, benzyl dialkyl ketal derivatives, acyl phosphine derivatives are preferred. Finoxide derivatives are particularly preferred.

Examples of photopolymerization initiators include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, p, p'-dichlorobenzophenone, p, p'-bisdiethylamino. Benzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1-hydroxy-cyclohexyl phenyl ketone, tetramethylthiuram monosulfide, thioxanthone, 2-chloro Thioxanthone, 2,4-dimethylthioxanthone, 2,2-dimethylpropioyl diphenylphosphine oxide, 2-methyl-2-ethyl Hexanoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,3,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6 -Trimethoxybenzoyl-diphenylphosphine oxide, 2,4,6-trichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylnaphthyl phosphonate, bi (Η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -finyl) titanium, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid Examples include acid, azobisisobutyronitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), benzoin peroxide, and di-tert-butyl peroxide.
Furthermore, examples of the photopolymerization initiator include photopolymerization initiators described on pages 65 to 148 of “Ultraviolet curing system” written by Kiyosuke Kato (published by General Technology Center Co., Ltd .: 1989). Can do.

These photopolymerization initiators can be used alone or in combination of two or more, and may be used in combination with a sensitizer.
Moreover, it is preferable that a photoinitiator does not raise | generate a thermal decomposition to 70 degreeC. Use of an initiator that causes thermal decomposition at 70 ° C. or lower is not preferable because there is a problem in product storage.
The amount of these photopolymerization initiators used in the curable composition (colored image forming composition) is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass. 10 mass% is especially preferable. If it is less than 0.5% by mass, it does not cure or the curing time is slow, and if it exceeds 20% by mass, precipitation or separation occurs with the lapse of time of dissolution, or performance such as ink strength and rubbing resistance after curing of the curable composition deteriorates. It is not preferable because it may cause

  The sensitizer is not activated by light irradiation alone, but when used together with the photopolymerization initiator, it is more effective than the photopolymerization initiator used alone, and amines are generally used. . The addition of amines increases the curing rate, primarily because hydrogen is supplied to the photopolymerization initiator by the action of hydrogen abstraction, and secondly, the generated radicals are combined with oxygen molecules in the atmosphere and are reactive. This is because the amine has an action of trapping oxygen dissolved in the composition.

Examples of sensitizers include amine compounds (aliphatic amines, amines containing aromatic groups, piperidine, reaction products of epoxy resins and amines, triethanolamine triacrylate, etc.), urea compounds (allylthiourea, o-tolylthio). Urea), sulfur compounds (sodium diethyl dithiophosphate, soluble salts of aromatic sulfinic acid, etc.), nitrile compounds (N, N-diethyl-p-aminobenzonitrile, etc.), phosphorus compounds (tri-n-butylphosphine, Sodium diethyldithiophosphide), nitrogen compounds (Michler ketone, N-nitrisohydroxylamine derivatives, oxazolidine compounds, tetrahydro-1,3-oxazine compounds, formaldehyde or acetaldehyde and diamine condensates), chlorine compounds (carbon tetrachloride) , Hexachloroethane, etc.), and the like.
The usage-amount in the curable composition of a sensitizer is 0-10 mass% normally, 0.1-10 mass% is preferable and 0.2-5 mass% is especially preferable.
The selection and combination of the photoinitiator and the sensitizer, and the blending ratio may be appropriately selected depending on the ultraviolet curing monomer used and the apparatus used.

  In the case of irradiating ultraviolet rays or visible light to polymerize the monomer, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a xenon lamp, a chemical lamp, or the like can be used as the light source.

-Other ingredients-
The curable composition of the present invention may contain other components appropriately selected according to the purpose, as described above, within a range that does not impair the effects of the present invention.
Examples of the other components include known additives such as solvents, polymers, surface tension adjusters, storage stabilizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, and pH adjusters. .

The solvent can be used to improve the polarity, viscosity, surface tension, solubility of oil-soluble dyes, conductivity adjustment, and printing performance of the curable composition.
Examples of the solvent include water, a low boiling point organic solvent, and a high boiling point organic solvent.
The low boiling point organic solvent is an organic solvent having a boiling point of 100 ° C. or lower. The low-boiling organic solvent is desirably not used in consideration of environmental pollution, but when used, it is preferable to use a highly safe one. A solvent having high safety is a solvent having a high management concentration (an index indicated by a work environment evaluation standard), preferably 100 ppm or more, and more preferably 200 ppm or more.
For example, alcohols, ketones, esters, ethers, hydrocarbons and the like can be mentioned. Specific examples include methanol, 2-butanol, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran and the like.
The high boiling organic solvent is an organic solvent having a boiling point higher than 100 ° C. The high-boiling organic solvent preferably has a boiling point of 150 ° C. or higher, more preferably 170 ° C. or higher.
Examples include polyhydric alcohols, esters of aliphatic carboxylic acids, phosphoric esters, hydrocarbons, and the like. Specific examples include diethylene glycol, trimethylolpropane, dibutyl phthalate, and 2-ethylhexyl benzoate. And alkylnaphthalene.
Depending on the purpose, these can be either liquid or solid at room temperature.
The solvent may be used alone or in combination.
The amount used in the curable composition is preferably from 0 to 20% by mass, more preferably from 0 to 10% by mass, and particularly preferably substantially free from contained. The term “substantially free” refers to the case where the material used is not intentionally added except for the main components, that is, those contained as impurities.

The polymer can be used for adjusting the polarity and viscosity of the curable composition, improving the solubility of the oil-soluble dye, adjusting the adhesion of the curable composition after curing to the recording material, and adjusting the light resistance. The polymer may be dissolved in the curable composition or may be a fine dispersion, but is preferably dissolved from the viewpoint of storage stability and discharge performance of the curable composition.
When the polymer is dissolved in the curable composition, those having high compatibility with dyes and monomers are preferable, and the weight average molecular weight is preferably 50000 or less, more preferably 20000 or less, from the viewpoint of hardly causing increase in the viscosity of the ink. 10,000 is particularly preferred.
For example, vinyl polymer, polyurethane, polyester and the like can be mentioned. Specifically, polybutyl acrylate, poly (isobutyl methacrylate-hydroxyethyl acrylate) (copolymerization mass ratio 95: 5), poly (isopropyl acrylate-tetrahydrofurfuryl acrylate). ) (Copolymerization mass ratio 70:30), poly (butyl methacrylate-N-methoxymethylacrylamide) (copolymerization mass ratio 80:20), polybutylacrylate-polydimethylsiloxane block copolymer (copolymerization mass ratio 90: 10).
When the polymer is a fine dispersion, it is essential that the polymer is not substantially dissolved in the monomer, and it is preferable that the polymer does not swell or does not swell.
The particle size of the dispersion in the curable composition is preferably 1 μm or less, more preferably 0.5 μm or less, and particularly preferably 0.1 μm or less. For example, vinyl polymer fine particles, polyurethane fine particles, polyester fine particles, urethane-vinyl composite particles and the like can be mentioned. Specifically, poly (acrylonitrile-ethyl acrylate-ethylene glycol dimethacrylate) (copolymerization mass ratio 60: 37: 3). ), Poly (styrene-butadiene) (copolymerization mass ratio 50:50), and the like.
The polymer may be used alone or in combination. The amount used in the curable composition is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and particularly preferably 0 to 20% by mass.

  The storage stabilizer is used to suppress undesired polymerization during storage, and is used that dissolves in the curable composition. Examples include quaternary ammonium salts, hydroxyamines, cyclic amides, nitriles, substituted ureas, heterocyclic compounds, organic acids, hydroquinones, hydroquinone monoethers, organic phosphines, copper compounds, etc. Specific examples include benzyltrimethylammonium chloride, diethylhydroxylamine, benzothiazole, 4-amino-2,2,6,6-tetramethylpiperidine, citric acid, hydroquinone monobutyl ether, and copper naphthenate. The amount of the storage stabilizer used is preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and particularly preferably 0.01 to 0.2% by mass.

As for the surface tension adjusting agent, ultraviolet absorber, antioxidant, fading preventing agent, and pH adjusting agent, those described in JP-A No. 2001-181549 may be used.
It is essential that the conductive salts are dissolved in the curable composition, and examples include potassium thiocyanate, lithium nitrate, ammonium thiocyanate, dimethylamine hydrochloride and the like.
By setting the curable composition of the present invention as described above, light resistance and ozone resistance can be imparted, and a cured product having excellent light resistance and ozone resistance after curing can be formed.

It is preferable to contain 0.1-20 mass parts of the said phthalocyanine compound of the said invention in 100 mass parts of solid content of the coloring image forming composition of this invention, and it is more preferable to contain 0.2-10 mass parts.
Further, in the colored image forming composition of the present invention, other pigments may be used in combination with the phthalocyanine compound. When using 2 or more types of pigment | dyes together, it is preferable to make the sum total of content of a pigment | dye into the said range.
The viscosity of the colored image forming composition of the present invention, particularly the ink for inkjet recording, is preferably 40 cp or less. The surface tension is preferably 20 mN / m to 70 mN / m.
Viscosity and surface tension are various additives, such as those mentioned above or other viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents It can be adjusted by adding a rust inhibitor, a dispersant and a surfactant.

The colored image forming composition of the present invention can be used not only for forming a single color image but also for forming a full color image. In particular, it can be suitably used as an ink for inkjet recording.
In order to form a full-color image, a magenta tone ink and a yellow tone ink can be used, and a cyan tone ink having a different cyan dye from the phthalocyanine compound of the present invention can be used in combination. Further, in order to adjust the color tone, a black color tone ink may be further used.

Any yellow dye that can be applied to the colored image forming composition can be used.
For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components); for example, coupler components Azomethine dyes having open-chain active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

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

Any cyan dye applicable to the colored image forming composition can be used in combination with the compound of the present invention.
For example, aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components; for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes, oxonol dyes, Polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

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

  The colored image forming composition of the present invention is suitable for recording on any recording material such as plain paper, coated paper, plastic film and the like, and image receiving material for ink jet recording.

[Inkjet recording method]
The ink jet recording method of the present invention is characterized in that an image is formed using the colored image forming composition used for ink jet recording.
That is, 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, for example, JP-A-8-169172 and JP-A-8-27693. JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153789, JP-A-10-217473, JP-A-10-235995. No. 10-337947, No. 10-217597, No. 10-337947, etc., such as inkjet exclusive paper, film, electrophotographic co-paper, cloth, glass, metal, ceramics, etc. Form.

  The ink jet recording method of the present invention is characterized in that the colored image forming composition of the present invention is used for recording on an image receiving material to form an image, and among these, dispersed ink and active energy curable ink are preferable.

When the colored image forming composition of the present invention is used for inkjet applications, there is no limitation on the inkjet recording method, and there are known methods, for example, a charge control method for discharging ink using electrostatic attraction, and vibration of a piezo element. Drop-on-demand method using pressure (pressure pulse method), acoustic ink jet method that converts electrical signals into acoustic beams, irradiates ink, and ejects ink using radiation pressure, and heats the ink to form bubbles In addition, it is used in a thermal ink jet system that uses the generated pressure.
The inkjet recording method includes a method of ejecting many low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method used is included.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to these Examples at all. In the following, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified.

(Synthesis Example 1) << Synthesis of C-1 >>
Compound C-1 was synthesized according to the following synthesis scheme.

<Synthesis of C-1-3 (C-1 precursor)>
1.50 g of glycine ethyl ester hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.50 g of triethylamine were dissolved in 20 ml of acetonitrile (AR). This solution was cooled to 0 ° C., and 3.22 g of the following compound C-1-4 synthesized by the method described in JP-A No. 2003-213168 (paragraph numbers [0215] and [0216]) was added in portions. The temperature was raised to room temperature, and after stirring for 1 hour, the reaction solution was poured into 20 g of water to crystallize a crude product of C-1-3. After dissolving this crude product in ethyl acetate, 3.5 g of C-1-3 was obtained by adding hexane and crystallizing (yield 88%).

<Synthesis of C-1-1 (C-1 precursor)>
4.0 g of C-1-3 obtained above, 0.45 g of copper (II) chloride, 0.4 g of lithium acetate, and 0.4 g of acetic acid are suspended in 20 ml of n-octanol and heated to 120 ° C. Stir for another 3 hours. After confirming the disappearance of the raw materials, the reaction solution was returned to room temperature and added to 100 ml of methanol to obtain C-1-2 crude crystals. The crude crystals were separated by filtration and dried, mixed with 5.0 g of sodium hydroxide, 20 ml of methanol and 20 ml of water, and heated to reflux for 3 hours. The obtained reaction solution was added to 200 ml of an aqueous solution containing 5 ml of 12M hydrochloric acid to crystallize a crude product of C-1-1. This crude crystal was dissolved in DMAc (dimethylacetamide), and then methanol was added to crystallize to obtain 2.71 g of C-1-1 (yield 77%).

<Synthesis of C-1>
1.55 g of C-1-1, 0.83 g of ethyl bromoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.69 g of potassium carbonate were dissolved in 20 ml of DMAc and stirred at 120 ° C. for 3 hours. After the reaction, 100 ml of water was added to crystallize the crude product of C-1. The crude crystals were separated by filtration, dissolved in ethyl acetate, and then crystallized by adding methanol to obtain 1.50 g of the desired product C-1 (yield 80%).
Λmax of the compound in ethyl acetate was 607 nm, and εmax was 3.40 × 10 ⁴ . The obtained compound was confirmed to be the target compound C-1 by MALDI TOF-MS and elemental analysis. The analysis result of MALDI TOF-MS was 189.121.

(Synthesis Example 2) << Synthesis of C-2 >>
In the synthesis of Compound C-1 of Synthesis Example 1, the reaction was performed in the same manner as the synthesis of C-1 of Synthesis Example 1 except that 0.91 g of ethyl 2-bromopropionate was used instead of ethyl bromoacetate. 1.60 g of the target product C-2 was obtained (yield 80%).
Λmax of the compound in ethyl acetate was 607 nm, and εmax was 3.40 × 10 ⁴ . The obtained compound was confirmed to be the target compound C-2 by MALDI TOF-MS and elemental analysis. The analysis result of MALDI TOF-MS was 1947.25.

(Synthesis Example 3) << Synthesis of C-3 >>
In the synthesis of Compound C-1 of Synthesis Example 1, the reaction was performed in the same manner as the synthesis of C-1 of Synthesis Example 1 except that 1.04 g of methyl 2-bromohexanoate was used instead of ethyl bromoacetate. 1.54 g of the target product C-3 was obtained (yield 76%).
Λmax of the compound in ethyl acetate was 607 nm, and εmax was 3.75 × 10 ⁴ . The obtained compound was confirmed to be the target compound C-3 by MALDI TOF-MS and elemental analysis. The analysis result of MALDI TOF-MS was 2059.37.

(Synthesis Example 4) << Synthesis of C-33 >>
Compound C-33 was synthesized according to the following synthesis scheme.

<Synthesis of C-33-4 (C-33 precursor)>
17.3 g of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 24.5 g of 2-ethylhexyl thioglycolate were dissolved in 200 ml of dimethyl sulfoxide. To this solution, 12.7 g of sodium carbonate was gradually added. After completion of the exotherm, the reaction solution was kept at 60 ° C. and stirred for 2 hours. After confirming the disappearance of the raw materials, the reaction solution was added to 500 ml of water and extracted with ethyl acetate to obtain a crude product of C-33-4. This was used in the next reaction as it was.

<Synthesis of C-33-3 (C-33 precursor)>
To a 100 ml acetic acid solution of C-33-4 (36.31 g in crude form) synthesized above and 1.32 g of disodium tungstate dihydrate was added dropwise 37 ml of hydrogen peroxide. After the end of heat generation, the mixture is stirred at 70 ° C. for 30 minutes. Thereafter, the reaction was stopped by adding the reaction solution to 300 ml of water. The target product was extracted with ethyl acetate, and the organic layer was washed with water and brine and concentrated under reduced pressure. Since the reaction product was a mixture of the desired sulfoxide compound and a by-product sulfone compound, the desired sulfoxide compound was isolated by column chromatography (yield 21 g, yield 55%).

<Synthesis of C-33-2 (C-33 precursor)>
23.81 g of C-33-3 synthesized earlier, 2.89 g of copper chloride, 1.95 g of lithium acetate and 1.95 g of acetic acid were suspended in 100 ml of 2-ethylhexanol and stirred at 130 ° C. for 30 minutes. After completion of the reaction, the reaction solution was added to 200 ml of methanol to crystallize the desired product. The obtained crude product was dissolved in DMAc, crystallized by adding isopropanol, filtered and dried to obtain 12.5 g of the desired product C-33-2 (yield 53%).

<Synthesis of C-33-1 (C-33 precursor)>
After suspending 3.0 g of C-33-2 synthesized earlier, 4 g of sodium hydroxide and 10 ml of water in 50 ml of methanol, the mixture was heated to 80 ° C. and stirred for 2 hours. The disappearance of the raw materials was confirmed by TLC and reverse phase TLC. Thereafter, the reaction solution was added to a 200 ml solution of 2 ml concentrated hydrochloric acid to crystallize the desired product. The obtained crude product was dissolved in DMAc, crystallized by adding ethyl acetate, filtered and dried to obtain 1.6 g of the desired product C-33-1 (yield 66%).

<Synthesis of C-33>
1.00 g of the compound C-33-1 synthesized above, 1.04 g of ethyl 2-bromohexanoate, and 0.69 g of potassium carbonate were dissolved in 20 ml of DMAc, and the mixture was stirred at 120 ° C. for 3 hours. After the reaction, 100 ml of water was added to crystallize a crude product of C-33. The crude crystals were filtered off, dissolved in DMAc, crystallized by adding isopropanol, filtered and dried to obtain 0.95 g of the desired product C-33 (yield 63%).
Λmax of the compound in ethyl acetate was 607 nm, and εmax was 3.52 × 10 ⁴ . The obtained compound was confirmed to be the target compound C-33 by MALDI TOF-MS and elemental analysis.

(Synthesis Example 5) << Synthesis of C-37 >>
1.18 g of compound C-37-1 obtained by the method described in JP 2002-256167 A [0149] and [0150], 0.87 g of ethyl 4-bromobutyrate, and 0.69 g of potassium carbonate in 20 ml of DMAc. Dissolved and stirred at 120 ° C. for 3 hours. After the reaction, 100 ml of water was added to crystallize a crude product of C-35. The crude crystals were separated by filtration, dissolved in acetone, and crystallized by adding methanol to obtain 1.06 g of the desired product C-37 (yield 65%).
Λmax of the compound in ethyl acetate was 600 nm, and εmax was 3.65 × 10 ⁴ . The obtained compound was confirmed to be the target compound C-35 by MALDI TOF-MS and elemental analysis. The analysis result of MALDI TOF-MS was 1639.50.

Synthesis Example 6 Synthesis of C-40
Compound C-40 was synthesized according to the following synthesis scheme.

<Synthesis of C-40-3 (C-40 precursor)>
15.0 g of glycine ethyl ester hydrochloride and 11.0 g of triethylamine were dissolved in 50 ml of pyridine. After cooling this solution with ice water, 21.0 g of trimellitic anhydride chloride was gradually added. Thereafter, the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, the reaction mixture was added to 500 ml of water to crystallize the desired product C-40-3 (yield 22.0 g, yield 76%).

<Synthesis of C-40-2 (C-40 precursor)>
The previously synthesized 11.7 g of C-40-3, 23.6 g of urea, 3.23 g of copper chloride, and 0.98 g of ammonium molybdate tetrahydrate were suspended in nitrobenzene. While stirring, the internal temperature was raised to 180 ° C., and the temperature was maintained as it was for 5 hours. After cooling to room temperature, 500 ml of water was added to the reaction solution to crystallize the crude product. The obtained crude product was collected by filtration, dissolved in DMAc, and crystallized by adding isopropanol to obtain the desired product (yield 5.5 g, yield 50%).

<Synthesis of C-40-1 (C-40 precursor)>
C-40-2 5.5 g synthesized earlier, 4 g of sodium hydroxide and 10 ml of water were suspended in 50 ml of methanol, heated to 80 ° C. and stirred for 2 hours. The disappearance of the raw materials was confirmed by TLC and reverse phase TLC. Thereafter, the reaction solution was added to a 100 ml aqueous solution of 4 ml of concentrated hydrochloric acid to crystallize the desired product. The obtained crude product was dissolved in DMAc, crystallized by adding ethyl acetate, collected by filtration, and dried to obtain 2.5 g of the desired product C-40-1 (yield 66%).

<Synthesis of C-40>
1.04 g of the previously synthesized C-40-1, 0.91 g of ethyl 3-bromopropionate and 0.69 g of potassium carbonate were dissolved in 20 ml of DMAc and stirred at 120 ° C. for 3 hours. After the reaction, 100 ml of water was added to crystallize a crude product of C-40. The crude crystals were separated by filtration, dissolved in DMAc, and crystallized by adding methanol to obtain 1.0 g of the desired product C-40 (yield 70%).
Λmax of the compound in ethyl acetate was 605 nm, and εmax was 3.75 × 10 ⁴ . The obtained compound was confirmed to be the target compound C-40 by MALDI TOF-MS, elemental analysis.

(Synthesis Example 7) <Synthesis of Polymer Solution PA-01>
22 parts of methyl ethyl ketone and 8.3 parts of 2-propanol were added to a 200 ml three-necked flask replaced with nitrogen gas. After raising the temperature to 65 ° C., 0.17 part of azobisvaleronitrile (V-65) was added. Next, a mixed solution of 35 parts of n-butyl acrylate, 15 parts of 2-hydroxyethyl acrylate, 0.42 parts of n-dodecanethiol, 22 parts of methyl ethyl ketone, and 8.3 parts of 2-propanol was dropped over 2 hours. did. After the subsequent reaction for 2 hours, 0.088 part of the V-65 was post-added, and the temperature was raised to 73 ° C. After a further 2 hours of reaction, an intended polymer solution (PA-1) having a solid content concentration of 45% was obtained.

[Example 1]
<Preparation of colored image forming composition (A-1)>
A mixed solution of 16 parts of ethyl acetate, 2.7 parts of the polymer solution (PA-1) (solid content 50%), and 0.45 parts of the phthalocyanine compound (oil-soluble dye) C-1 was prepared. Separately, a mixed solution of 18 parts of water and 0.4 part of Emar 20C (Kao Corporation) was prepared. After the two mixed solutions were combined, they were mixed and emulsified with a homogenizer (manufactured by Nippon Seiki). The emulsion was concentrated at 30 ° C. under reduced pressure to remove ethyl acetate to prepare a colored image forming composition (A-1) having a solid content of 17%. It was 110 nm when the volume average particle diameter of the colored fine particles in the colored image forming composition was measured with LB-500 (manufactured by HORIBA Ltd.).

<Preparation of ink (DA-01)>
The following materials were mixed and filtered through a 0.45 μm filter to prepare an aqueous inkjet recording ink (DA-01).
Colored image forming composition (A-1) 50 parts Diethylene glycol 5 parts Glycerin 18 parts Triethanolamine 1 part Olfine E1010 1 part (surfactant manufactured by Air Products)
・ Amount of water to be 100 parts

[Examples 2 to 11]
<Preparation of colored image forming composition (A-2 to 6, 15, 33, 38 to 40)>
In the preparation of the colored image forming composition (A-1) of Example 1, instead of the phthalocyanine compound (oil-soluble dye) C-1, the exemplified compounds C-2 to 6, 15, 33, and 38 to 40 are used. A colored image forming composition was obtained in the same manner as in Example 1 except that it was used.

<Preparation of ink (DA-02 to 06, 15, 33, 38 to 40)>
In the preparation of the ink (DA-01), the colored image forming composition (A-2 to 6, 15, 33, 38 to 40) was used instead of the colored fine particle dispersion (A-1). Ink was prepared in the same manner as Ink (DA-01).

[Example 12]
<Preparation of ink (UVA-01)>
The following components were mixed with stirring to produce an inkjet recording cyan ink (UVA-01).
Monomer: caprolactone-modified dipentaerythritol hexaacrylate (DPCA60: manufactured by SARTOMER) 6.0 g
Monomer: 1,6-hexanediol diacrylate (HDDA: manufactured by Daicel UCB) 14.0 g
Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide mixture (manufactured by Ciba Specialty Chemicals) 0.6 g
・ Phthalocyanine compound (oil-soluble dye) C-1 0.4g

[Examples 13 and 14]
<Preparation of ink (UVA-02 to 03)>
In Example 12, the ink (UVA) of Example 12 was used except that the phthalocyanine compound (oil-soluble dye) (C-2, C-3) was used instead of the phthalocyanine compound (oil-soluble dye) (C-1). In the same manner as in (-01), inks (UVA-02 to 03) were produced.

[Comparative Examples 1-3]
<Preparation of ink (DB-101 to 103)>
In Example 1, except that the following phthalocyanine compound (oil-soluble dye) (C-101 to 103) was used instead of the phthalocyanine compound (oil-soluble dye) (C-1), the ink (DA-) in Example 1 was used. Ink was prepared in the same manner as in 01).

-Image recording and evaluation-
The ink (DA-01 to 06, DB-101 to 103) obtained as described above is filled into a cartridge of an ink jet printer MC-2000 (manufactured by EPSON Corporation), and is used for the PPC plain paper. Images were recorded on inkjet paper photo glossy paper “Imagai” (Fuji Photo Film Co., Ltd.) and evaluated as follows. The evaluation results are shown in Table 1.
The ink (UVA-01-03) obtained as described above was printed on art paper with an inkjet printer (printing density: 300 dpi, droplet ejection frequency: 4 kHz, number of nozzles: 64) and then a Deep UV lamp (manufactured by USHIO). The sample was exposed under the condition of SP-7) at an energy of 20 mj / m ² to obtain a print sample having a cyan density of about 1.0.
These samples were evaluated for durability and ozone resistance as shown below.

<Light resistance evaluation>
The photo glossy paper on which the image is formed is irradiated with xenon light (100,000 lx) for 7 days using a weather meter (Atlas C.165), and the image density before and after the xenon irradiation is measured using a reflection densitometer (X-Rite310TR). And was evaluated as a dye residual ratio (%). The reflection density was fixed at 1.0 and measured.

<Ozone resistance evaluation>
The photo glossy paper on which the image has been formed is stored for 7 days under the condition of ozone concentration of 0.5 ppm, and the image density before and after exposure to ozone is measured using a reflection densitometer (X-Rite310TR). ) Was evaluated.

<Solubility evaluation>
At the time of creating the colored image forming composition, 5 was excellent in solubility of the phthalocyanine compound (oil-soluble dye), 3 was the standard level, 1 was the level at which insolubles could be confirmed, Visual evaluation was performed in 5 stages, with each intermediate level being 4 and 2.

  As is apparent from the above results, it is possible to prepare a colored image forming composition and ink jet recording ink exhibiting light resistance and ozone resistance while maintaining high solubility from the phthalocyanine compound (pigment) of the present invention. I understand that I can do it.

Claims (5)

A phthalocyanine compound represented by the following general formula (1).

[In the general formula (1), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , —CONR ₁ R ₂ , —CO ₂ represents R ₁ or —COR ₁ . Z independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₁ and R ₂ are each independently 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 aryl group, substituted or unsubstituted Represents a heterocyclic group. One or more groups of Z, R ₁ and R ₂ include —CO ₂ — (CR ₃ R ₄ ) n—CO ₂ R ₅ — as a substituent. Here, R ₃ and R ₄ each independently represents a substituted or unsubstituted alkyl group or a hydrogen atom, R ₅ represents an alkyl group, n represents an integer of 1 to 20, and n is an integer of 2 or more. Sometimes a plurality of R ₃ and R ₄ may be the same or different. Y _{1 to} Y ₄ each independently represent a hydrogen atom or a monovalent substituent. _{a 1 ~a 4, b 1 ~b} 4 are each X ₁ to X _4, and represents the number of substituents Y ₁ to Y _4. a _{1 to} a ₄ each independently represents a number from 0 to 4, but all of them are not 0 at the same time. b ₁ ~b ₄ represents the number of independently 0-4. When a _{1 to} a ₄ and b _{1 to} b ₄ represent a number of 2 or more, the plurality of X _{1 to} X ₄ and Y _{1 to} Y ₄ may be the same or different. M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. ] The said general formula (1) is represented by the following general formula (2), The phthalocyanine compound of Claim 1 characterized by the above-mentioned.

[In the general formula _{(2), X 1 ~X 4} , M are respectively the X ₁ to X _4, M in the general formula (1) in the same meaning. a _{1 to} a ₄ each independently represents an integer of 1 or 2. ] A colored image forming composition comprising the phthalocyanine compound according to claim 1. The colored image forming composition according to claim 1, wherein the colored image forming composition is used for ink jet recording. An ink jet recording method comprising forming an image using the colored image forming composition according to claim 4.