JP2002285050A - Method for improving ozone resistance using phthalocyanine pigment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for improving ozone resistance, which method provides colored images and colored materials, applicable to various coloring compositions such as an ink composition for printing such as ink-jet, an ink sheet in a heat-sensitive transfer image forming material, a toner for electrophotography, a color composition for a color filter used in an LCD, PPD and CCD, and a dye solution for dyeing various fibers and excellent in hue and fastness (particularly ozone resistance). SOLUTION: The ozone resistance of the colored image materials is improved by using a phthalocyanine pigment having an oxidation potential nobler than 1.0 V (vs SCE) represented by general formula (1). A concrete example is represented by formula (2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for improving ozone resistance of a colored image material using a phthalocyanine dye, and more particularly to an ink jet recording method having improved ozone resistance applied to a water-soluble ink for cyan ink jet recording.

[0002]

2. Description of the Related Art In recent years, as an image recording material, a material mainly for forming a color image has been mainly used. Specifically, an ink jet recording material, a thermal transfer type image recording material, and an electrophotographic recording material are used. Materials, transfer-type silver halide photosensitive materials, printing inks, recording pens, and the like are actively used. In the display, LCD and PDP,
In imaging equipment, color filters are used in electronic components such as CCDs. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixture method or subtractive color mixture method are used in order to reproduce or record a full-color image. The fact is that there are no robust dyes that have feasible absorption properties and can withstand various use conditions.
Improvement is strongly desired. The inkjet recording method is
Due to the low material cost, high-speed recording, low noise at the time of recording, and easy color recording, it is rapidly spreading and further developing.

[0003] Ink jet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with an image information signal. In the ejection method, pressure is applied by a piezo element. A method in which bubbles are generated in ink by heat to eject droplets, a method using ultrasonic waves, and a method in which droplets are sucked and ejected by electrostatic force. Further, as the ink for inkjet recording, an aqueous ink, an oil-based ink, or a solid (melt-type) ink is used.

[0004] The dyes used in such inks for ink jet recording have good solubility or dispersibility in solvents, high density recording is possible,
Good hue, light, heat, environmental active gas (N
O _x, it is robust to other SO _x, etc.) of an oxidizing gas such as ozone, it has excellent fastness to water and chemicals, ensure good fixing property less blurring on an image-receiving material, the ink It is required that the slag be excellent in preservability, be non-toxic, have high purity, and be available at low cost.

In particular, there is a strong demand for a dye which has a good cyan hue and is robust against light and an active gas in the environment, especially an oxidizing gas such as ozone.

As a cyan dye skeleton used in a water-soluble ink for ink-jet recording, phthalocyanine and triphenylmethane are typical.

The most widely reported and utilized representative phthalocyanine dyes include phthalocyanine derivatives classified into the following. Direct Blue 86 or Direct B
copper phthalocyanine dyes such as lue 199 [for example,
_{Cu-Pc- (SO 3 Na)} m: a mixture of m = 1 to 4].

[0008] JP-A-62-190273, JP-A-6-190273
3-28690, JP-A-63-306075, JP-A-63-30076, JP-A-2-131983,
JP-A-3-122171, JP-A-3-200883
Phthalocyanine dyes [for example, Cu-Pc- (SO ₃ Na) _m (SO ₂ NH
₂ ) _n : a mixture of m + n = 1 to 4].

JP-A-63-210175, JP-A-6-210175
Phthalocyanine dyes described in JP-A-3-37176, JP-A-63-304071, JP-A-5-171085, WO 00/08102 [for example, Cu-Pc- (CO ₂
H) _m (CONR ₁ R ₂ ) _n : m + n = 0 to 4]

JP-A-59-30874, JP-A-Hei 1-30
126381, JP-A-1-190770, JP-A-6-190770
-16982, JP-A-7-82499, JP-A-8-824
No. 34942, JP-A-8-60053, JP-A-8-1
No. 13745, JP-A-8-310116, JP-A-10
No. 1400063, JP-A-10-298463, JP-A-11-29729, JP-A-11-320921,
EP173476A2, EP468649A1, E
P559309A2, EP596383A1, DE
No. 3,411,476, US Pat.
/ 13009 Patent, phthalocyanine dyes described in GB2341868A No., etc. _{[e.g., Cu-Pc- (SO 3 H} )
_m (SO ₂ NR ₁ R ₂ ) _n : m + n = 0 to 4 and m
$ 0]

JP-A-60-208365, JP-A-6-208365
1-22772, JP-A-6-57653, JP-A-8-576
No. 60052, JP-A-8-295819 and JP-A-10
JP-A-130517, JP-A-11-72614, JP-A-11-515047, JP-A-11-515048,
EP 196901 A2, WO 95/29208,
WO 98/49239, WO 98/49240
No., WO 99/50363, WO 99/6733
No. 4, etc. [e.g., Cu-Pc
-(SO ₃ H) _l (SO ₂ NH ₂ ) _m (SO ₂ NR ₁ R ₂ ) _n : l
+ M + n = 0 to 4]

JP-A-59-22967, JP-A-61-1986
185576, JP-A-1-95093, JP-A-3
No. 195,783, EP 649881 A1, WO 0
No. 08/08101, WO 00/08103, etc. [phthalocyanine dyes such as Cu-Pc- (SO ₂ NR
₁ R ₂ ) _n : n = 1 to 5]

[0013] Direc, which is currently widely used in general,
t Blue 86 or Direct Blue 199
The phthalocyanine dyes described in the above documents and the like are characterized by having superior light fastness compared to magenta and yellow, but have a greenish hue under acidic conditions and are unsuitable for cyan ink. is there. Therefore, when these dyes are used as cyan ink, it is most suitable to use them under neutral to alkaline conditions.
However, even if the ink is neutral to alkaline, the hue of the printed matter may significantly change when the recording material to be used is acidic paper.

Further, oxidizing gases such as nitrogen oxide gas and ozone, which are often taken up as an environmental problem these days, cause discoloration and decoloration to a greenish taste, and at the same time decrease the print density.

On the other hand, for triphenylmethane,
Although the hue is good, it is very poor in light fastness, ozone gas fastness and the like.

In the future, when the field of use is expanded and widely used for exhibitions such as advertisements, it is often exposed to light or an active gas in the environment. active gas fastness and the environment so that the dye and the ink composition having excellent fastness to (NO _x, other sO _x such as an oxidizing gas such as ozone) are desired more and more strongly. However, it is extremely difficult to find cyan dyes (eg, phthalocyanine dyes) and cyan inks that meet these requirements at a high level.

Hitherto, as a phthalocyanine dye provided with ozone gas resistance, JP-A-3-103484,
JP-A-4-39365, JP-A-2000-303909
However, at present, none of them has been able to achieve both the hue and the fastness of light and oxidizing gas. In particular, there have been no reports on the properties of dyes, which serve as guidelines for ozone gas resistance.

[0018]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention provides 1) an ink composition for printing such as ink jet, an ink sheet for a heat-sensitive transfer type image forming material, and an electronic device, which provide a colored image or a colored material having excellent hue and fastness (particularly, ozone resistance). Photo toner,
Provide a method for improving ozone resistance, which can be applied to various color compositions such as color compositions for color filters used in LCDs, PPDs and CCDs, and dyeing solutions for dyeing various fibers.
2) In particular, ink-jet recording using an ink for ink-jet recording, which has a good hue due to the use of a phthalocyanine dye derivative, and can form an image having high robustness to light and an active gas in the environment, particularly ozone gas. The aim is to provide a method.

[0019]

The present inventors have studied in detail a phthalocyanine dye derivative having good hue, high light fastness and high gas fastness (particularly, ozone gas).
Dyes having a specific oxidation potential, which have not been known, and dyes having a specific dye structure (introducing a specific type of substituent at a specific substitution position at a specific substitution position), preferably a dye represented by the following general formula (I) It has been found that the above problems can be solved by the phthalocyanine dye represented by formula (II) or (III), and the present invention has been completed. The means for solving the above problems are as follows. That is,

(1) An oxidation potential of 1.0 V (vs. SC
A method for improving ozone resistance of a colored image material, which comprises using a phthalocyanine dye which is more noble than E).

(2) The method for improving ozone resistance according to the above (1), wherein the phthalocyanine dye is a phthalocyanine dye represented by the following general formula (I).

[0022]

Embedded image

In the formula (I), X₁, X_Two, X_ThreeAnd X_FourHaso
Each independently represents -SO-Z₁, -SO_Two-Z₁, -SO_TwoN
R₁R_TwoOr a sulfo group. Where Z₁Replaces
Or unsubstituted alkyl group, substituted or unsubstituted cycle
Loalkyl group, substituted or unsubstituted alkenyl group,
Substituted or unsubstituted aralkyl group, substituted or unsubstituted
Represents an aryl group or a substituted or unsubstituted heterocyclic group.
You. R₁Is a hydrogen atom, a substituted or unsubstituted alkyl
Group, substituted or unsubstituted cycloalkyl group,
Or unsubstituted alkenyl group, substituted or unsubstituted ara
Alkyl group, substituted or unsubstituted aryl group, or
Represents a substituted or unsubstituted heterocyclic group, _TwoReplaces
Or unsubstituted alkyl group, substituted or unsubstituted cycle
Loalkyl group, substituted or unsubstituted alkenyl group,
Substituted or unsubstituted aralkyl group, substituted or unsubstituted
An aryl group or a substituted or unsubstituted heterocyclic group
Represents Y₁, Y_Two, Y_ThreeAnd Y_FourAre each independently water
Element atom, halogen atom, alkyl group, cycloalkyl
Group, alkenyl group, aralkyl group, aryl group, hetero
Ring group, cyano group, hydroxyl group, nitro group, amino
Group, alkylamino group, alkoxy group, aryloxy
Group, amide group, arylamino group, ureido group, sulf
Amoylamino group, alkylthio group, arylthio group,
Alkoxycarbonylamino group, sulfonamide group,
Rubamoyl group, alkoxycarbonyl group, heterocyclic oxo
Si group, azo group, acyloxy group, carbamoyloxy
Group, silyloxy group, aryloxycarbonyl group,
Reeloxycarbonylamino group, imide group, heterocycle
Thio, phosphoryl, acyl, carboxyl,
Or a sulfo group, each of which further has a substituent.
Is also good. a₁~ A_Four, B₁~ B_FourIs X₁~ X_Fourand
Y₁~ Y_FourRepresents the number of substituents of₁~ A_FourAre independently
Represents an integer from 0 to 4, but all become 0 at the same time
There is no. b₁~ B_FourEach independently represents an integer of 0 to 4;
Note that a₁~ A_FourAnd b₁~ B_FourRepresents an integer of 2 or more
, Multiple X₁~ X_FourAnd Y₁~ Y_FourAre the same even if
It may be different. M is a hydrogen atom, a metal element or
Of oxides, hydroxides or halides of

(3) The method for improving ozone resistance according to the above (2), wherein the phthalocyanine dye represented by the general formula (I) is a phthalocyanine dye represented by the following general formula (II).

[0025]

Embedded image

In the formula (II), X₁₁, X₁₂, X₁₃And X₁₄
Are each independently -SO-Z₁₁, -SO_Two-Z₁₁, −
SO_TwoNR₁₁R₁₂Or a sulfo group. Z₁₁Replace
Or an unsubstituted alkyl group or a substituted or unsubstituted
Chloroalkyl group, substituted or unsubstituted alkenyl group,
Substituted or unsubstituted aralkyl group, substituted or unsubstituted
A substituted aryl group or a substituted or unsubstituted heterocycle
Represents a group. R₁₁Is a hydrogen atom, a substituted or unsubstituted
Alkyl group, substituted or unsubstituted cycloalkyl group,
Substituted or unsubstituted alkenyl group, substituted or unsubstituted
An aralkyl group, a substituted or unsubstituted aryl group,
Or a substituted or unsubstituted heterocyclic group;₁₂Is
Substituted or unsubstituted alkyl group, substituted or unsubstituted
A cycloalkyl group, substituted or unsubstituted alkenyl
Group, substituted or unsubstituted aralkyl group, substituted or
An unsubstituted aryl group, or a substituted or unsubstituted
Represents a ring group. Y₁₁, Y₁₂, Y₁₃, Y₁₄, Y₁₅, Y₁₆,
Y₁₇And Y₁₈Are each independently a hydrogen atom, a halogen
Atom, alkyl group, cycloalkyl group, alkenyl group,
Aralkyl, aryl, heterocyclic, cyano, aralkyl
Droxyl group, nitro group, amino group, alkylamino
Group, alkoxy group, aryloxy group, amide group, ant
Amino group, ureido group, sulfamoylamino group,
Alkylthio group, arylthio group, alkoxycarbonyl
Ruamino group, sulfonamide group, carbamoyl group,
Oxycarbonyl group, heterocyclic oxy group, azo group, reed
Ruoxy group, carbamoyloxy group, silyloxy group,
Aryloxycarbonyl group, aryloxycarbonyl
Amino group, imide group, heterocyclic thio group, phosphoryl
Group, acyl group, carboxyl group, or sulfo group
However, each may further have a substituent. a₁₁~ A
₁₄Is X₁₁~ X₁₄Represents the number of substituents of
It represents an integer from 0 to 2, but all become 0 at the same time.
There is no. Note that a₁₁~ A ₁₄Represents two, two X's
₁₁~ X₁₄May be the same or different. M is
Hydrogen atom, metal element or its oxide, hydroxide or
Is a halide.

(4) The formula (I) or the formula (I
In the phthalocyanine dye represented by I), the phthalocyanine dye has at least four ionic hydrophilic groups in one molecule (where the ionic hydrophilic group is a carboxyl group, a sulfo group or a quaternary ammonium group). (2) or (3), wherein the groups are the same or different.

(5) The method for improving ozone resistance according to the above (2), wherein the phthalocyanine dye represented by the general formula (I) is a phthalocyanine dye represented by the following general formula (III).

[0029]

Embedded image

In the formula (III), X_{twenty one}, X_{twenty two}, X_{twenty three}And X
_{twenty four}Are each independently -SO-Z_{twenty one}, -SO_Two-Z_{twenty one},
-SO_TwoNR_{twenty one}R_{twenty two}Or a sulfo group. Z_{twenty one}Is
Substituted or unsubstituted alkyl group, substituted or unsubstituted
Cycloalkyl group, substituted or unsubstituted alkenyl
Group, substituted or unsubstituted aralkyl group, substituted or
An unsubstituted aryl group, or a substituted or unsubstituted
Represents a ring group. R_{twenty one}Is a hydrogen atom, substituted or unsubstituted
Alkyl group, substituted or unsubstituted cycloalkyl
Group, substituted or unsubstituted alkenyl group, substituted or
Unsubstituted aralkyl group, substituted or unsubstituted aryl
A substituted or unsubstituted heterocyclic group;
_{twenty two}Is a substituted or unsubstituted alkyl group,
Unsubstituted cycloalkyl group, substituted or unsubstituted alkyl
Phenyl, substituted or unsubstituted aralkyl, substituted
Or unsubstituted aryl group, or substituted or unsubstituted
Represents a heterocyclic group. a_{twenty one}~ A_{twenty four}Is X_{twenty one}~ X_{twenty four}
And independently represent an integer of 0 to 2
However, they do not all become 0 at the same time. Note that a_{twenty one}~
a _{twenty four}Represents two, two X's_{twenty one}~ X_{twenty four}Are the same
But they may be different. M is a hydrogen atom, a metal element or
Is an oxide, hydroxide or halide thereof.

(6) A method for improving ozone resistance of a colored image material, comprising using the ink composition for inkjet recording containing the phthalocyanine dye described in any of the above (1) to (5). (7) Ink jet recording characterized by forming an image on an image receiving material having an ink image receiving layer containing white inorganic pigment particles on a support, using the ink composition for ink jet recording described in (6) above. Method.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [Phthalocyanine dye] In the present invention, the oxidation potential is 1.0 V
A phthalocyanine dye which is more noble than (vs. SCE) is used. The more noble the oxidation potential is, the more preferable the oxidation potential is more than 1.1 V (vs. SCE), and the most preferable is the one having nobleness more than 1.15 V (vs. SCE).

The value of the oxidation potential (Eox) can be easily measured by those skilled in the art. Regarding this method, for example,
"New Instrumental" by Delahay
Methods in Electrochemist
ry ”(1954 Interscience Pu)
Blishers) and A. J. Bard et al., "El
electrochemical Methods ”(19
80 (John Wiley & Sons), Akira Fujishima et al., "Electrochemical Measurement Method" (1984, published by Gihodo Shuppan).

[0034] Specifically, oxidation potential, in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate, a test sample 1 × 10 ^-4 ~1 × 10 ^{- After} dissolving ⁶ mol / liter, the value is measured as a value for SCE (saturated calomel electrode) using cyclic voltammetry or DC polarography. Although this value may be deviated by about several tens of mil volts due to the influence of the liquid potential difference or the liquid resistance of the sample solution, the reproducibility of the potential can be guaranteed by inserting a standard sample (for example, hydroquinone). Further, a suitable supporting electrolyte and solvent can be selected depending on the oxidation potential and solubility of the test sample. For the supporting electrolytes and solvents that can be used, see Akira Fujishima et al.
It is described on pages 101-118.

The value of Eox indicates the ease of transfer of electrons from the sample to the electrode, and the value is large (the oxidation potential is noble).
The more the electron is transferred from the sample to the electrode, the more difficult it is to oxidize. In relation to the structure of the compound, the introduction of an electron-withdrawing group makes the oxidation potential more noble, and the introduction of an electron-donating group makes the oxidation potential lower. In the present invention, in order to reduce the reactivity with ozone as an electrophile, it is desirable to introduce an electron-withdrawing group into the phthalocyanine skeleton to make the oxidation potential more noble. Therefore, using the Hammett's substituent constant σp value, which is a measure of the electron withdrawing or electron donating property of the substituent, the X ₁ , X ₂ , X ₃ , X ₄ , X ₁₁ , X ₁₂ , X _{12 13,} X _14,
It can be said that by introducing a substituent having a large σp value such as a sulfinyl group, a sulfonyl group, and a sulfamoyl group, such as X ₂₁ , X ₂₂ , X ₂₃ , and X ₂₄ , the oxidation potential can be made more noble.

The Hammett's substituent constant σp value will be described briefly. Hammett's rule is 193 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
5 years L. P. A rule of thumb proposed by Hammett, which is widely accepted today. The substituent constants determined by the Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, "Lange '
s Handbook of Chemistry, 12th edition, 1979 (Mc Graw-Hill) and extra edition of "The Field of Chemistry", 122, 96-103, 19
Detailed in 1979 (Nankodo).

In the present invention, a phthalocyanine dye represented by the above formula (I) is preferably used as the phthalocyanine dye. Hereinafter, the phthalocyanine dye represented by the general formula (I) will be described in detail.

In the general formula (I), X ₁ , X ₂ , X
₃ and X ₄ are each independently -SO-Z ₁ , -SO ₂ -Z
₁ represents -SO ₂ NR ₁ R ₂ or a sulfo group. Here, as described above, when a _{1 to} a ₄ representing the number of substituents represent an integer of 2 or more, a plurality of X ₁ , X ₂ , X ₃ and X ₄ may be the same or different. And each independently represents any one of the above groups.

Z ₁ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, Represents an unsubstituted heterocyclic group, particularly preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted hetero group are preferable. Ring groups are most preferred.

R ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group,
A substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group,
Represents a substituted or unsubstituted heterocyclic group, particularly preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, among which a hydrogen atom, a substituted alkyl group , A substituted aryl group and a substituted heterocyclic group are most preferred.

R ₂ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, Represents an unsubstituted heterocyclic group, particularly preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted hetero group are preferable. Ring groups are most preferred.

The substituted or unsubstituted alkyl group represented by R ₁ , R ₂ and Z ₁ is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent include Z ₁ , R ₁ , R
_The same substituents as those when ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ can further have a substituent can be mentioned. Among them, a hydroxyl group, an alkoxy group, a cyano group, a halogen atom and an ionic hydrophilic group are preferred.

A substituted or unsubstituted cycloalkyl group represented by R ₁ , R ₂ and Z ₁ is
A cycloalkyl group having 5 to 30 carbon atoms is preferred.
Examples of the substituent include the following Z ₁ , R ₁ , R ₂ , Y ₁ ,
The same substituents as those when Y ₂ , Y ₃ and Y ₄ can further have a substituent are mentioned. Among them, a hydroxyl group, an alkoxy group, a cyano group, a halogen atom and an ionic hydrophilic group are preferred.

An alkenyl group having a substituent represented by R ₁ , R ₂ and Z ₁ or an unsubstituted alkenyl group is included.
The alkenyl group is preferably an alkenyl group having 2 to 30 carbon atoms. Examples of the substituent include Z described below.
_The same substituents as described above when ₁ , R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ can further have a substituent can be mentioned. Among them, a hydroxyl group, an alkoxy group, a cyano group, a halogen atom and an ionic hydrophilic group are preferred.

An aralkyl group having a substituent represented by R ₁ , R ₂ and Z ₁ or an unsubstituted aralkyl group is included.
The aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. Examples of the substituent include Z described below.
_The same substituents as described above when ₁ , R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ can further have a substituent can be mentioned. Among them, a hydroxyl group, an alkoxy group, a cyano group, a halogen atom and an ionic hydrophilic group are preferred.

As the substituent of the aryl group represented by R ₁ , R ₂ and Z ₁ , the following Z ₁ , R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ further have a substituent. Are the same as the substituents when possible. Preferred substituents include a halogen atom, a heterocyclic group, a cyano group, a hydroxyl group,
Nitro, carboxyl, acylamino, ureido, sulfamoylamino, alkyloxycarbonyl, alkyloxycarbonylamino, sulfonamide, sulfamoyl, carbamoyl, sulfonyl, acyloxy, carbamoyloxy, imide Group, heterocyclic thio group, acyl group, sulfo group, quaternary ammonium group, among which heterocyclic group, cyano group, carboxyl group, acylamino group, sulfonamide group, sulfamoyl group, carbamoyl group, carbamoyl group, sulfonyl group, imide group , Acyl group, sulfo group, quaternary ammonium group is preferable, cyano group, carboxyl group, sulfamoyl group,
Carbamoyl group, sulfonyl group, imide group, acyl group,
Sulfo groups and quaternary ammonium groups are more preferred.

The heterocyclic group represented by R ₁ , R ₂ and Z ₁ is preferably a 5- or 6-membered heterocyclic group, which may be further condensed. Further, it may be an aromatic hetero ring or a non-aromatic hetero ring. Hereinafter, the heterocyclic group represented by R ₁ , R ₂ and Z ₁ will be exemplified in the form of a heterocyclic ring by omitting the substitution position. However, the substitution position is not limited. Substitution at the 2-, 3-, and 4-positions is 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 as described above, and pyridine, pyrazine, pyrimidine, pyridazine,
Triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole. They may have a substituent, and examples of the substituent include the following Z ₁ , R ₁ , R ₂ , Y ₁ ,
The same substituents as those when Y ₂ , Y ₃ and Y ₄ can further have a substituent are mentioned. Preferred substituents are the same as the preferred substituents of the aryl group, and more preferred substituents are the same as the more preferred substituents of the aryl group.

Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group. , Nitro, amino, alkylamino, alkoxy, aryloxy, amide, arylamino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl Group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl Group, acyl group, Represents a ruboxyl group or a sulfo group, each of which may further have a substituent.

Among them, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, an ureido group, a sulfonamide group, a carbamoyl group,
Preferred are a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfo group, particularly preferred are a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, and a sulfo group, and most preferred is a hydrogen atom.

Z ₁ , R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄
When is a group capable of further having a substituent, it may further have a substituent as described below.

A halogen atom (eg, a chlorine atom or a bromine atom), a linear or branched alkyl group having 1 to 30 carbon atoms,
An aralkyl group having 7 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a linear or branched alkynyl group having 2 to 30 carbon atoms, a linear or branched cycloalkyl group having 3 to 30 carbon atoms, and 3 carbon atoms -30 linear or branched cycloalkenyl groups, specifically (for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), aryl group ( For example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), a heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl,
-Pyrimidinyl, 2-benzothiazolyl), a cyano group,
Hydroxyl group, nitro group, carboxy group, amino group,
Alkyloxy group (for example, methoxy, ethoxy, 2-
Methoxyethoxy, 2-methanesulfonylethoxy),
Aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamido, benzamido, -(3-t-butyl-4-hydroxyphenoxy) butanamide), an alkylamino group (for example, methylamino, butylamino, diethylamino, methylbutylamino), an anilino group (for example, phenylamino, 2-chloroanilino, ureido group ( For example, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino), alkylthio group (eg, methylthio, octylthio, 2-phenoxy) Ruthio), an arylthio group (eg, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), an alkyloxycarbonylamino group (eg, methoxycarbonylamino), a sulfonamide group (eg, methanesulfone) Amide, benzenesulfonamide, p-toluenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl),
Sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyloxycarbonyl Groups (eg, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy groups (eg, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo groups (eg, phenylazo, 4-methoxyphenylazo, -Pivaloylaminophenylazo, 2-
Hydroxy-4-propanoylphenylazo), an acyloxy group (eg, acetoxy), a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg,
Trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N-
Succinimide, N-phthalimido), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-
Pyridylthio), a sulfinyl group (eg, 3-phenoxypropylsulfinyl), a phosphonyl group (eg,
Phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic group (eg, carboxyl Group, sulfo group,
And quaternary ammonium groups).

The halogen atom represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group has 1 to 1 carbon atoms.
30 alkyl groups are preferred. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group. Examples of alkyl groups include methyl, ethyl, butyl, isopropyl, t
-Butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

The cycloalkyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include alkenyl groups having a substituent and unsubstituted alkenyl groups. The alkenyl group is preferably an alkenyl group having 2 to 30 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group, an allyl group and the like.

The aralkyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. The aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms.
Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group is preferably an aryl group having 7 to 30 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include a substituted heterocyclic group and an unsubstituted heterocyclic group. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group. Examples of the substituent include:
Includes ionic hydrophilic groups. Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group and a 2-furyl group.

The alkylamino groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include an alkylamino group having a substituent and an unsubstituted alkylamino group. The alkylamino group is preferably an alkylamino group having 1 to 30 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The alkoxy groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms. Examples of the substituent include an alkoxy group, a hydroxyl group and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group and a 3-carboxypropoxy group.

The aryloxy groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group and an o-methoxyphenoxy group.

The amide group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an amide group having a substituent and an unsubstituted amide group. The amide group has 2 to 3 carbon atoms.
An amide group of 0 is preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the amide group include an acetamido group, a propionamido group, a benzamide group, and a 3,5-disulfobenzamide group.

The arylamino groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 30 carbon atoms. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

The ureido groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include ureido groups having a substituent and unsubstituted ureido groups. The ureido group is preferably a ureido group having 1 to 30 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

[0065] The Y _1, Y _2, Y ₃ and Y ₄ sulfamoylamino group represented by include sulfamoylamino group and an unsubstituted sulfamoylamino group having a substituent. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include an N, N-dipropylsulfamoylamino group.

The alkylthio groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 30 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

The arylthio groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 30 carbon atoms. Examples of the substituent include an alkyl group and an ionic hydrophilic group. Examples of the arylthio group include a phenylthio group and a p-tolylthio group.

The alkoxycarbonylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonamide groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include a sulfonamide group having a substituent and an unsubstituted sulfonamide group. The sulfonamide group is preferably a sulfonamide group having 1 to 30 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

The carbamoyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

The sulfamoyl groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group and an aryl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group, a di- (2-hydroxyethyl) sulfamoyl group, and a phenylsulfamoyl group.

The sulfonyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkylsulfonyl group which may have a substituent and an arylsulfonyl group which may have a substituent. Examples of the sulfonyl group include a methylsulfonyl group and a phenylsulfonyl group.

The alkoxycarbonyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The heterocyclic oxy group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a substituted heterocyclic oxy group and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having a 5- or 6-membered heterocyclic ring. Examples of the substituent include a hydroxyl group and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.

The azo groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include azo groups having a substituent and unsubstituted azo groups. Examples of the azo group include a p-nitrophenylazo group.

The acyloxy groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include an acyloxy group having a substituent and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 30 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

The carbamoyloxy group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

The silyloxy groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include a silyloxy group having a substituent and an unsubstituted silyloxy group. Examples of the substituent include an alkyl group. Examples of the silyloxy group include a trimethylsilyloxy group.

The aryloxycarbonyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The aryloxycarbonylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The imide groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include an imide group having a substituent and an unsubstituted imide group. Examples of the imide group include an N-phthalimido group and an N-succinimido group.

The heterocyclic thio groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include a substituted heterocyclic thio group and an unsubstituted heterocyclic thio group. The heterocyclic thio group preferably has a 5- or 6-membered heterocyclic ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

The phosphoryl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group. Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.

The acyl groups represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include an acyl group having a substituent and an unsubstituted acyl group. The acyl group has 1 to 1 carbon atoms.
Two acyl groups are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The phthalocyanine dye represented by formula (I) preferably has an ionic hydrophilic group.
Further, one molecule of the phthalocyanine dye preferably has at least four ionic hydrophilic groups, and more preferably, the ionic hydrophilic group is a sulfo group and / or a carboxyl group. Those having at least four carboxyl groups are particularly preferred.

A _{1 to} a ₄ and b _{1 to} b ₄ each represent X ₁ to
X ₄ represents the number of substituents of Y _{1 to} Y ₄ ; a _{1 to} a ₄ each independently represent an integer of 0 to 4; b _{1 to} b ₄ each independently represent an integer of 0 to 4; Here, when a _{1 to} a ₄ and b _{1 to} b ₄ represent an integer of 2 or more, a 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 independently represent an integer of 0 to 4 satisfying the relationship of a ₁ + b ₁ = 4, and particularly preferably, a ₁ represents 1 or 2, and b ₁ represents 3 or This is a combination representing 2, and among them, a ₁ represents 1 and b ₁ represents 3.

A ₂ and b ₂ each independently represent an integer of 0 to 4 satisfying the relationship of a ₂ + b ₂ = 4, and particularly preferably, a ₂ represents 1 or 2, and b ₂ represents 3 or This is a combination representing 2, and among them, a ₂ represents 1 and b ₂ represents 3.

A ₃ and b ₃ each independently represent an integer of 0 to 4 that satisfies the relationship of a ₃ + b ₃ = 4, and particularly preferably, a ₃ represents 1 or 2, and b ₃ represents 3 or It is a combination that represents 2, and among them, the combination in which a ₃ represents 1 and b ₃ represents ₃ is most preferable.

A ₄ and b ₄ each independently represent an integer of 0 to 4 satisfying the relationship of a ₄ + b ₄ = 4, and particularly preferably, a ₄ represents 1 or 2, and b ₄ represents 3 or It is a combination that represents 2, and among them, a combination in which a ₄ represents 1 and b ₄ represents 3 is most preferable.

M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof. Preferred examples of M include a hydrogen atom and metal atoms such as Li, Na,
K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, C
o, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, C
d, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi and the like. Examples of the oxide include VO and GeO. The hydroxides include Si (OH) ₂ , Cr (OH) ₂ , Sn (O
H) _{2 and the} like. Further, as the halide,
AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, ZrCl and the like. Among them, particularly preferred are Cu, Ni, Zn, Al and the like, and most preferred is Cu.

Further, Pc is linked via L (a divalent linking group).
(Phthalocyanine ring) is a dimer (for example, Pc-ML)
-M-Pc) or a trimer, and M at that time may be the same or different.

The divalent linking group represented by L is an oxy group-
O-, thio group -S-, a carbonyl group -CO-, a sulfonyl group -SO ₂ -, -NH- imino group, or a methylene group -CH ₂ - are preferred.

Particularly preferred combinations of the phthalocyanine dyes represented by formula (I) are as follows.

X _{1 to} X ₄ are each independently -SO
₂ -Z or -SO ₂ NR ₁ R ₂ is particularly preferred.

Z ₁ is each independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Of these, a substituted alkyl group, a substituted aryl group and a substituted hetero group are preferred. Ring groups are most preferred.

R ₁ is independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
Among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are most preferred.

R ₂ is independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Of these, a substituted alkyl group, a substituted aryl group and a substituted hetero group are preferred. Ring groups are most preferred.

It is more preferred that at least one of R ₁ and R ₂ has an ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent.

Y _{1 to} Y ₄ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group,
Preferred are a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfo group, particularly preferred are a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, and a sulfo group, and most preferred is a hydrogen atom.

A _{1 to} a ₄ are each independently preferably 1 or 2, and particularly preferably 1. b ₁
To b ₄ are each independently preferably 3 or 2, and particularly preferably 3.

M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof, particularly Cu, N
i, Zn, and Al are preferable, and particularly, Cu is most preferable. The phthalocyanine dye represented by the general formula (I) preferably contains an ionic hydrophilic group, and more preferably has at least 4 or more ionic hydrophilic groups in one molecule of the phthalocyanine dye. The hydrophilic group is preferably a sulfo group, and among them, those having at least four sulfo groups are most preferred.

As for the preferable combination of the substituents of the compound represented by the general formula (I), a compound in which at least one of various substituents is the above-mentioned preferable group is preferable, and more various substituents are Compounds that are preferred groups are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

Among the phthalocyanine dyes represented by the general formula (I), phthalocyanine dyes having the structure represented by the general formula (II) are more preferable. Hereinafter, the phthalocyanine dye represented by formula (II) of the present invention will be described in detail.

In the general formula (II), X₁₁~ X₁₄,
Y₁₁~ Y₁₈Is X in the general formula (I) ₁~ X_Four, Y₁~ Y_FourWhen
Each has the same meaning, and preferred examples are also the same. Also,
M has the same meaning as M in formula (I), and preferred examples are also the same.
It is like.

In the general formula (II), a₁₁~ A₁₄Is 4 ≦ a₁₁+
a₁₂+ A₁₃+ A₁₄1 independent of each other within the range of ≦ 8
Or an integer of 2 and particularly preferably 4 ≦ a₁₁+ A₁₂
+ A ₁₃+ A₁₄≦ 6, and among them, particularly preferred is
a₁₁= A₁₂= A₁₃= A₁₄= 1.

Among the phthalocyanine dyes represented by the general formula (II), particularly preferred combinations of substituents are as follows.

X _{11 to} X ₁₄ each independently represent -S
O ₂ -Z ₁₁ or -SO ₂ NR ₁₁ R ₁₂ are particularly preferred.

Z ₁₁ is independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Of these, a substituted alkyl group, a substituted aryl group and a substituted hetero group are preferred. Ring groups are most preferred.

R ₁₁ is preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
Among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are most preferred.

R ₁₂ is independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Of these, a substituted alkyl group, a substituted aryl group and a substituted hetero group are preferred. Ring groups are most preferred.

It is more preferable that at least one of R ₁₁ and R ₁₂ has an ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent.

Y _{11 to} Y ₁₈ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group And a sulfo group are preferable, and particularly, a hydrogen atom, a halogen atom, a cyano group, a carboxyl group,
And a sulfo group are preferred, and a hydrogen atom is most preferred.

Preferably, a _{11 to} a ₁₄ are each independently 1 or 2, and particularly preferably all are 1.

M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof, particularly Cu, N
i, Zn, and Al are preferable, and particularly, Cu is most preferable.

Among the phthalocyanine dyes represented by the general formula (I), the phthalocyanine dyes having the structure represented by the general formula (III) are more preferable. The phthalocyanine dye represented by formula (III) of the present invention will be described in detail below.

In the general formula (III), X _{21 to} X ₂₄
Has the same meaning as X _{1 to} X ₄ in formula (I), respectively.
Preferred examples are also the same. M has the same meaning as M in the general formula (I), and preferred examples are also the same.

In the general formula (II), a₁₁~ A₁₄Is 4 ≦ a₁₁+
a₁₂+ A₁₃+ A₁₄1 independent of each other within the range of ≦ 8
Or an integer of 2 and particularly preferably 4 ≦ a₁₁+ A₁₂
+ A ₁₃+ A₁₄≦ 6, and among them, particularly preferred is
a₁₁= A₁₂= A₁₃= A₁₄= 1.

Among the phthalocyanine dyes represented by the general formula (III), particularly preferred combinations of substituents are as follows.

X _{21 to} X ₂₄ each independently represent -S
O ₂ —Z ₂₁ or —SO ₂ NR ₂₁ R ₂₂ is particularly preferred.

Z ₂₁ is preferably each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Among them, a substituted alkyl group, a substituted aryl group and a substituted hetero group are preferred. Ring groups are most preferred.

R ₂₁ is preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
Among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are most preferred.

R ₂₂ is independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Of these, a substituted alkyl group, a substituted aryl group and a substituted hetero group are preferred. Ring groups are most preferred.

It is more preferable that at least one of R ₂₁ and R ₂₂ has an ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent.

It is preferable that a _{21 to} a ₂₄ are each independently 1 or 2, and it is particularly preferable that all of them are 1.

M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof, especially Cu, N
i, Zn, and Al are preferable, and particularly, Cu is most preferable.

Among the phthalocyanine dyes represented by the general formula (I), phthalocyanine dyes having the structure represented by the general formula (III) are more preferable. The phthalocyanine dye represented by formula (III) of the present invention will be described in detail below.

In the general formula (III), X _{21 to} X ₂₄
Has the same meaning as X _{1 to} X ₄ in formula (I), respectively.
Preferred examples are also the same. M has the same meaning as M in the general formula (I), and preferred examples are also the same.

In the general formula (II), a₁₁~ A₁₄Is 4 ≦ a₁₁+
a₁₂+ A₁₃+ A₁₄1 independent of each other within the range of ≦ 8
Or an integer of 2 and particularly preferably 4 ≦ a₁₁+ A₁₂
+ A ₁₃+ A₁₄≦ 6, and among them, particularly preferred is
a₁₁= A₁₂= A₁₃= A₁₄= 1.

Of the phthalocyanine dyes represented by formula (III), particularly preferred combinations of substituents are as follows.

X _{21 to} X ₂₄ each independently represent -S
O ₂ —Z ₂₁ or —SO ₂ NR ₂₁ R ₂₂ is particularly preferred.

Z ₂₁ is preferably each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Among them, a substituted alkyl group, a substituted aryl group and a substituted hetero group are preferred. Ring groups are most preferred.

R ₂₁ is preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
Among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are most preferred.

R ₂₂ is independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Of these, a substituted alkyl group, a substituted aryl group and a substituted hetero group are preferred. Ring groups are most preferred.

More preferably, at least one of R ₂₁ and R ₂₂ has an ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent.

It is preferable that a _{21 to} a ₂₄ are each independently 1 or 2, and it is particularly preferable that all of them are 1.

M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof, particularly Cu, N
i, Zn, and Al are preferable, and particularly, Cu is most preferable.

The phthalocyanine dyes represented by formulas (II) and (III) preferably contain an ionic hydrophilic group, and have at least 4 or more ionic hydrophilic groups per molecule of the phthalocyanine dye. Is more preferable, and particularly preferably, the ionic hydrophilic group is a sulfo group,
Among them, those having at least four sulfo groups are most preferred.

As for the preferable combination of the substituents of the compounds represented by formulas (II) and (III), a compound in which at least one of various substituents is the above-mentioned preferable group is preferable. Compounds in which the substituents are the preferred groups are more preferred, and compounds in which all the substituents are the preferred groups are most preferred.

In order to improve the solubility or dispersibility in an aqueous medium, the compounds represented by the general formulas (I), (II) and (I)
The phthalocyanine dye represented by II) preferably has at least four or more ionic hydrophilic groups in the molecule. The ionic hydrophilic group as a substituent includes a sulfo group,
Includes carboxyl groups and quaternary ammonium. The carboxyl group and the sulfo group may be in the form of a salt. Examples of the counter ion forming the salt include an alkali metal ion (eg, sodium ion, potassium ion) and an organic cation (eg, tetramethylguanidinium ion). ) Is included. Among them, a sulfo group and a carboxyl group are preferred. It is particularly preferable that at least four or more sulfo groups and / or carboxyl groups are contained.

In general, it is known to use various phthalocyanine derivatives as ink compositions for ink jet recording. The phthalocyanine derivative represented by the above general formula (I) is inevitably substituted X
There are cases where n (n = 1 to 4) and Ym (m = 1 to 4) are substituted, and these substituted positional isomers are often regarded as the same derivative without being distinguished from each other.

The case where the structure is different in the phthalocyanine dyes defined in the present specification means that the substituents Xn (n = 1 to 4) and Ym (m =
This is either the case where the constituent atomic species of 1 to 4) are different, the case where the number is different or the case where the positions are different.

In the present invention, the compounds represented by the general formulas (I) and (I)
Derivatives having different structures (particularly, substitution positions) of the phthalocyanine dyes represented by I) and (III) are defined by classifying them into the following three types.

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

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

(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 a derivative of a phthalocyanine dye having a different structure (particularly, substitution position) is described, the above β-position substitution type, α-position substitution type, and α, β-position mixed substitution type are used. I do.

The phthalocyanine derivatives used in the present invention are described, for example, in Shirai-Kobayashi, co-authored by IPC, Inc., “Phthalocyanine-Chemistry and Function-” (P. 1-62),
C. C. Leznoff-A. B. P. Lever co-authored, VCH issued 'Phthalocyanines-P
rightsies and Application
s' (P. 1 to 54), etc., can be synthesized by a combination of methods similar thereto.

The phthalocyanine compounds of the present invention represented by the general formula (I) are disclosed in World Patents 00/17275 and 00/17275.
08103, 00/08101, 98/4185
3. As described in JP-A-10-36471, for example, the compound can be synthesized through a sulfonation, sulfonyl chloride, or amidation reaction of an unsubstituted phthalocyanine compound. In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonated 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 having different numbers of substituents and different substitution positions is always obtained. 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 groups cannot be specified,
The compound of the present invention can be obtained as a mixture containing several compounds having different numbers of substituents and different substitution positions.

As described above, 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 increased.
According to the above synthesis method, it is inevitable that a phthalocyanine dye having a small number of introduced electron-withdrawing groups, 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.

On the other hand, the phthalocyanine compound represented by the general formula (II) is, for example, a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following structural formula. The formula (I
V) or a 4-sulfophthalonitrile derivative (compound R) represented by the following structural formula and a metal derivative represented by the following general formula (IV): It can be derived from a sulfophthalocyanine compound.

[0152]

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In each of the above formulas, Xp represents the above formula (II)
X₁₁, X₁₂, X₁₃Or X₁₄Is equivalent to Also, Yq
Or Yq ′ is each of the above general formula (II)
Y₁₁, Y ₁₂, Y₁₃, Y₁₄, Y₁₅, Y₁₆, Y₁₇Or Y₁₈
Is equivalent to In the compound R, M ′ represents a cation.
You.

Formula (IV) M- (Y) d

In the general formula (IV), M has the same meaning as M in the general formulas (I) and (II), and Y is a monovalent or divalent group such as a halogen atom, an acetate anion, acetylacetonate or oxygen. And d is an integer of 1 to 4.

That is, according to the above synthesis method, a desired number of substituents can be introduced. In particular, when a large number of electron withdrawing groups are to be introduced in order to increase the oxidation potential as in the present invention, this synthesis method is extremely superior to the synthesis method described above as the synthesis method of the general formula (I). Things.

The metal derivatives represented by the general formula (IV) include Al, Si, Ti, V, Mn, Fe, Co, Ni,
Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, P
t, halide of Pb, carboxylic acid derivative, sulfate,
Nitrate, carbonyl compound, oxide, complex and the like can be mentioned. 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, and 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 amounts of the metal derivative represented by the general formula (IV) and the phthalonitrile compounds P to R are not particularly limited, but are preferably in a molar ratio of 1: 3 to 1: 6.

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, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylaminoethanol,
Examples include diethylaminoethanol, trichlorobenzene, chloronaphthalene, sulfolane, nitrobenzene, quinoline, and urea. The amount of the solvent used is 1 to 100 times by weight, preferably 5 to 20 times by weight of the phthalonitrile compound.

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 0.1 to 10 with respect to 1 mol of the phthalonitrile compound.
The molar amount is preferably 0.5 to 2 times.

The reaction temperature is 80 to 300 ° C., preferably 1 to 300 ° C.
The reaction is preferably performed at a reaction temperature in the range of 00 to 250 ° C, and particularly preferably in the reaction temperature range of 130 to 230 ° C. Below 80 ° C., the reaction rate is extremely slow.
If the temperature is higher than 300 ° C., the phthalocyanine compound may be decomposed.

The reaction time is 2 to 20 hours, preferably 5 to 20 hours.
The reaction is preferably performed within a reaction time of 15 hours.
It is particularly preferable to carry out the reaction within a reaction time of 10 to 10 hours. If the time is less than 2 hours, a large amount of unreacted raw material is present, and if the time is longer than 20 hours, the phthalocyanine compound may be decomposed.

The products obtained by these reactions can be processed according to a usual post-treatment method of an organic synthesis reaction and then purified or used without purification.

That is, for example, the product released from the reaction system is not purified, or recrystallized, and column chromatography (for example, gel permeation chromatography (SEPHADEX ^™ LH-20: Pharmacia)
) Can be provided alone or in combination.

Alternatively, after completion of the reaction, the reaction solvent is distilled off, or the residue is poured into water or ice without being distilled off, neutralized or liberated without neutralization, without purification or re-purification. It can be provided after performing an operation of purifying by crystallization, column chromatography or the like, alone or in combination.

After the completion of the reaction, the reaction solvent was distilled off.
Alternatively, the product is extracted with an organic solvent / water solution without neutralization by neutralizing with water or ice without distilling, or purified by crystallization or column chromatography. After the operations are performed alone or in combination, they can be provided.

The phthalocyanine compound represented by the above general formula (II) thus obtained is usually an isomer at each substitution position of Xp, which is represented by the following general formulas (a-1) to (a-
It is a mixture of compounds represented by 4).

[0168]

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[0169]

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That is, the general formulas (a-1) to (a-
The compound represented by 4) is a β-substituted type (2 and / or 3, 6 and / or 7, 10 and / or 11, 14
And / or a phthalocyanine dye having a specific substituent at the 15-position).

In the present invention, the compound of the general formula (II)
-Position substitution type. The α, β-position mixed substitution type compound is a mixture of compounds having different substituent positions and numbers, and the β-position substitution type compound is a mixture of compounds having different substituent positions. In the present invention, it has been found that in any of the substitution types, it is very important that the oxidation potential is more noble than 1.0 V (vs. SCE) for improving the robustness. It was completely unexpected from the prior art. Although the cause is unknown, the β-position substitution type tends to be superior to the α, β-position substitution substitution type in hue, light fastness, ozone gas resistance and the like.

Specific examples of the phthalocyanine dye represented by formula (I) or (II) (exemplified compounds 101 to 14)
3) is shown below, but the phthalocyanine dye used in the present invention is not limited to the following examples.

[0173]

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[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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[0179]

[Table 1]

[0180]

[Table 2]

[0181]

[Table 3]

[0182]

[Table 4]

[0183]

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The phthalocyanine dye represented by the general formula (I) can be synthesized according to the above-mentioned patent. The phthalocyanine dye represented by the general formula (II) can be synthesized, for example, by the method described in Japanese Patent Application No. 2001-24352. The starting materials, dye intermediates and synthetic routes are not limited by these.

The dyes of the present invention can be used as materials for forming images, particularly color images. Specifically, the dyes used in the present invention include, for example, ink-jet recording materials described in detail below, and heat-sensitive transfer image recording materials. Materials, pressure-sensitive recording materials, electrophotographic recording materials, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink jet recording materials, heat-sensitive transfer image recording materials, and electrophotographic systems. It is a recording material to be used, and more preferably an ink jet recording material. Also, U.S. Pat.
It can be applied to color filters used in solid-state imaging devices such as LCDs and CCDs described in JP-A-8501 and JP-A-6-35182 and dyeing solutions for dyeing various fibers. The dye of the present invention is used after adjusting physical properties such as solubility and heat transferability suitable for the intended use by a substituent.
Further, the dye of the present invention can be used in a uniform dissolved state, a dispersed dissolved state such as emulsified dispersion, or a solid dispersed state depending on the system used.

[Ink for Inkjet Recording] The ink for inkjet recording can be produced by dissolving and / or dispersing the phthalocyanine dye in a lipophilic medium or an aqueous medium. Preferably, an aqueous medium is used. If necessary, other additives are contained within a range that does not impair the effects of the present invention. As other additives, for example, an anti-drying agent (wetting agent),
Anti-fading agent, emulsion stabilizer, penetration enhancer, ultraviolet absorber,
Known additives such as preservatives, fungicides, pH adjusters, surface tension adjusters, defoamers, viscosity adjusters, dispersants, dispersion stabilizers, rust preventives, chelating agents and the like can be mentioned. These various additives are added directly to the ink liquid in the case of a water-soluble ink. When the oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but may be added to the oil phase or the aqueous phase during the preparation.

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

As the anti-drying agent, a water-soluble organic solvent having a lower vapor pressure than water is preferable. 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 And lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, and triethylene glycol monoethyl (or butyl) ether. , 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine and other heterocycles, 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. The above-mentioned drying inhibitors may be used alone or in combination of two or more. These drying inhibitors are present in the ink in an amount of 10 to 50% by weight.
It is preferred to contain.

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

The ultraviolet absorber is used for the purpose of improving the storability of an image. Examples of the ultraviolet absorber include JP-A-58-185677 and JP-A-61-90537.
Gazette, JP-A-2-782, 5-197070
Benzotriazole compounds described in JP-A-9-34057, JP-A-46-2784,
JP-A-5-194483, U.S. Pat. No. 32144
No. 63, etc., JP-B-48-30492, JP-B-56-21141,
Cinnamic acid-based compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-534
No. 27, No. 8-239368, No. 10-18
No. 2621, Japanese Translation of PCT International Publication No. 8-501291, and the like. Compounds described in No. 24239 and compounds emitting fluorescent light by absorbing ultraviolet light represented by stilbene-based and benzoxazole-based compounds, so-called fluorescent whitening agents, can also be used.

The anti-fading agent is used for the purpose of improving the storability of an image. As the anti-fading agent, various organic and metal complex-based anti-fading agents can be used. Hydroquinones as organic anti-fading agents,
Alkoxyphenols, dialkoxyphenols,
There are phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like, and metal complexes include nickel complexes and zinc complexes. More specifically, Research Disclosure No.
No. 17643, Sections VII I through J; 1516
2, the same No. No. 18716, left column, page 650; 36
No. 544, page 527; 307105, page 872,
No. Compounds described in the patent cited in US Pat. No. 15,162, and pages 127 to 13 of JP-A-62-215272.
The compounds included in the general formulas and the compound examples of representative compounds described on page 7 can be used.

Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate and sodium pyridinethione.
Examples include 1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one, and salts thereof. These are contained in the ink
It is preferred to use 1.00% by weight.

As the pH adjusting agent, the neutralizing agent (organic base, inorganic alkali) can be used. The pH
The adjuster is used for improving the storage stability of the ink-jet ink, and the ink-jet ink has a pH of 6 to 10.
It is preferably added for summer use, and more preferably added so as to have a pH of 7 to 10.

Examples of the surface tension modifier include nonionic, cationic and anionic surfactants. still,
The surface tension of the inkjet ink of the present invention is 25 to 7
0 mPa · s is preferred. Further, it is preferably 25 to 60 mN / m. The viscosity of the inkjet ink of the present invention is preferably 30 mPa · s or less. 20 mPa · s
It is more preferable to adjust as follows. Examples of surfactants include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfates Anionic surfactants such as ester salts, polyoxyethylene alkyl ethers,
Nonionic surfactants such as polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and oxyethylene oxypropylene block copolymer are preferred. Also, SURFYNOLS (Air Products & Ch), which is an acetylene-based polyoxyethylene oxide surfactant, is used.
chemicals) is also preferably used. Also, N,
Amine oxide type amphoteric surfactants such as N-dimethyl-N-alkylamine oxide are also preferable. Furthermore,
JP-A-59-157,636, pages (37) to (38), Research Disclosure No. 308119 (198
Those described as surfactants described in (9) can also be used.

As the defoaming agent, a fluorine-based or silicone-based compound, a chelating agent represented by EDTA, or the like can be used if necessary.

In the case where the phthalocyanine dye of the present invention is dispersed in an aqueous medium, JP-A-11-286637 and JP-A-2000-78139 disclose the phthalocyanine dye of the present invention.
No. 491, No. 2000-80259, Disperse colored fine particles containing a dye and an oil-soluble polymer in an aqueous medium as described in No. 2000-62370, and Japanese Patent Application Nos. 2000-78454 and 2000-78491.
As described in JP-A Nos. 2000-203856 and 2000-203857, it is preferable to disperse the dye of the present invention dissolved in a high-boiling organic solvent in an aqueous medium. The specific method for dispersing the dye of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive and the amount of use thereof are preferably those described in the above patent. it can. Alternatively, the azo dye may be dispersed in the form of fine particles as a solid. At the time of dispersion, a dispersant or a surfactant can be used. Examples of the dispersing device include a simple stirrer or impeller stirring method, an in-line stirring method, a mill method (for example, a colloid mill, a ball mill, a sand mill, an attritor, a roll mill, an agitator mill, etc.), an ultrasonic method, a high-pressure emulsifying dispersion method (a high-pressure homogenizer). Specific examples of commercially available devices include a Gaulin homogenizer, a microfluidizer, and DeBEE2000.)
Can be used. Regarding the method of preparing the above ink for ink jet recording, besides the above-mentioned patents, JP-A-5-148436, JP-A-5-295512, and JP-A-7-29553
97541, 7-82515, 7-11858
No. 4, JP-A-11-286637, Japanese Patent Application No. 2000-8
The details are described in each of the publications of No. 7539 and can also be used for preparing the ink for inkjet recording of the present invention.

As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec.
-Butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol),
Polyhydric 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 (For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether 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, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, Acetone). The water-miscible organic solvent may be used in combination of two or more.

Ink for Inkjet Recording 10 of the Invention
In 0 parts by weight, the phthalocyanine dye is preferably contained in an amount of 0.2 to 10 parts by weight. Further, other dyes may be used in combination with the phthalocyanine dye in the inkjet ink of the present invention. When two or more dyes are used in combination, the total content of the dyes is preferably within the above range.

The ink-jet recording ink of the present invention comprises:
It can be used not only for monochromatic image formation but also for full-color image formation. To form a full-color image,
Magenta color ink, cyan color ink, and yellow color ink can be used, and further black color ink may be used to adjust the color.

As the applicable yellow dye, any yellow dye can be used. For example, aryl or hetarylazo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, open-chain active methylene compounds as coupling components (hereinafter referred to as coupler components); Azomethine dyes having open-chain active methylene compounds; 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 applicable magenta dye can be used. For example, aryl or hetenylazo dyes having phenols, naphthols, anilines and the like as coupler components; azomethine dyes having pyrazolones and pyrazolotriazoles 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 and xanthene dyes; condensed polycycles such as quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; Dyes and the like can be mentioned.

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

Each of the above dyes may exhibit each color of yellow, magenta and cyan only after a part of the chromophore is dissociated, and the counter cation in that case may be an inorganic metal such as an alkali metal or ammonium. It may be a cation, an organic cation such as a pyridinium or quaternary ammonium salt, or a polymer cation having such a partial structure. Examples of applicable black materials include disazo, trisazo, and tetraazo dyes as well as carbon black dispersions.

[Ink-jet recording method] The ink-jet recording method of the present invention provides a known image-receiving material, that is, plain paper or resin-coated paper, for example, by applying energy to the ink for ink-jet recording described in JP-A-8-169172. JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238873, JP-A-10-
No. 153989, No. 10-217473, No. 10-235995, No. 10-337947, No. 10-217597, No. 10-33794
An image is formed on ink-jet dedicated paper, film, electrophotographic common paper, fabric, glass, metal, porcelain, and the like described in Japanese Patent Publication No. 7 and the like.

In forming an image, a polymer latex compound may be used in combination for the purpose of imparting gloss and water resistance and improving weather resistance. Regarding the time of applying the latex compound to the image receiving material, before, after, or simultaneously with the application of the colorant, it may be performed at the same time. It may be in the ink, or may be used as a liquid material of the polymer latex alone. Specifically, Japanese Patent Application 2000-36
No. 3090, No. 2000-315231, No. 2000
-354380, 2000-343944, 2
000-2688952 can be preferably used.

The recording paper and recording film used for ink-jet printing using the ink of the present invention will be described below. The support in recording paper and recording film is made of chemical pulp such as LBKP, NBKP, G
P, PGW, RMP, TMP, CTMP, CMP, CG
It consists of mechanical pulp such as P, waste paper pulp such as DIP,
If necessary, conventionally known pigments, binders, sizing agents,
Mix additives such as fixing agent, cationic agent, paper strength agent,
Those manufactured by various apparatuses such as a fourdrinier paper machine and a round paper machine can be used. In addition to these supports, any of synthetic paper and plastic film sheet may be used. The support has a thickness of 10 to 250 μm and a basis weight of 10 to 250 g.
/ M ² is desirable. The support may be provided with an ink receiving layer and a back coat layer as they are, or after providing a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, and then providing an ink receiving layer and a back coat layer. Further, the support may be subjected to a flattening treatment using a calender such as a machine calender, a TG calender, and a soft calender. In the present invention, as the support,
Paper and plastic films laminated on both sides with a polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene, and copolymers thereof) are more preferably used. It is preferable to add a white pigment (for example, titanium oxide, zinc oxide) or a coloring dye (for example, cobalt blue, ultramarine, neodymium oxide) to the polyolefin.

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

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. Such as water-soluble polymers, styrene butadiene latex,
A water-dispersible polymer such as an acrylic emulsion can be used. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peel resistance of the ink receiving layer.

The ink receiving layer may contain a mordant, a water-proofing agent, a light fastness improving agent, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For this purpose, a polymer mordant is preferably used. Polymer mordants are described in JP-A-48-28325 and JP-A-54-74430.
No. 54-124726, No. 55-22766,
No. 55-142339, No. 60-23850, No. 6
Nos. 0-23851, 60-23852, 60-2
No. 3853, No. 60-57836, No. 60-6064
No. 3, No. 60-118834, No. 60-122940
No. 60-122941, No. 60-122942
No. 60-235134, JP-A-1-161236
Nos. 2,484,430 and 25,485.
Nos. 64, 3148061, 3309690, 4115124, 4124386, 41938
No. 00, No. 4,273,853, No. 4,282,305, and No. 4,450,224. JP 1
An image receiving material containing a polymer mordant described on pages 212 to 215 of 161236 is particularly preferred. When the polymer mordant described in the publication is used, an image having excellent image quality is obtained, and the light fastness of the image is improved.

The water-proofing agent is effective for making the image water-resistant. As such a water-proofing agent, a cationic resin is particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethylene imine,
Examples thereof include polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. The content of these cationic resins is preferably 1 to 15% by weight based on the total solid content of the ink receiving layer, and particularly
It is preferably from 10 to 10% by weight.

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

The surfactant functions as a coating aid, a release improver, a slipperiness improver, or an antistatic agent. Regarding the surfactant, JP-A-62-1746.
No. 3, No. 62-183457.
An organic fluoro compound may be used instead of the surfactant. Preferably, the organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorinated surfactant, an oily fluorinated compound (for example, fluorinated oil), and a solid fluorinated compound resin (for example, ethylene tetrafluoride resin). Regarding the organic fluoro compound, JP-B-57-9053 (columns 8 to 17) and JP-A-61-2
Nos. 0994 and 62-135826. Other additives added to the ink receiving layer include a pigment dispersant, a thickener, a defoamer, a dye, a fluorescent whitening agent,
Preservatives, pH adjusters, matting agents, hardening agents and the like can be mentioned. The ink receiving layer may be a single layer or two layers.

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

The aqueous binder contained in the back coat layer includes styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin And water-soluble polymers such as carboxymethylcellulose, hydroxyethylcellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. Other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.

A polymer latex may be added to the constituent layers (including the back coat layer) of the ink jet recording paper and the recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. Polymer latex is described in JP-A-62-245258 and JP-A-62-1.
It is described in each publication of 316648 and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to the layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the back coat layer.

The ink of the present invention is not limited to an ink jet recording method, and is a known method, for example, a charge control method for discharging ink by using electrostatic attraction, a drop-on-demand method using vibration pressure of a piezo element. (Pressure pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate the ink, and the ink is ejected using a radiation pressure, and a pressure is generated by heating the ink to form bubbles. Used in thermal ink jet systems and the like. The ink jet recording method uses a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality by using a plurality of inks having substantially the same hue and different densities, or a colorless transparent ink. The method is included.

[0218]

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

Example 1 After adding deionized water to the following components to make 1 liter,
The mixture was stirred for 1 hour while heating at 0 to 40 ° C. Then K
Adjust the pH to 9 with OH 10mol / L, and adjust the average pore size.
The mixture was filtered under reduced pressure through a 0.25 μm microfilter to prepare a cyan ink liquid.

[Composition of Ink Liquid A] Cyan dye (113) of the present invention 25.0 g diethylene glycol 20 g glycerin 120 g diethylene glycol monobutyl ether 230 g 2-pyrrolidone 80 g triethanolamine 17.9 g benzotriazole 0.06 g Surfynol TG 8.5 g PROXEL XL2 1.8 g

Ink liquids B and C were prepared in the same manner as in preparation of ink liquid A, except that the phthalocyanine dye was changed as shown in Table 5 below. At this time, ink liquids 101 and 102 were prepared using comparative compounds 1 and 2 in Table 5 as ink liquids for comparison.

When the dye was changed, the dye was used such that the amount of the dye was equimolar to the ink liquid A. When two or more dyes were used in combination, they were used in equimolar amounts.

(Image Recording and Evaluation) Each of the above examples (ink liquids A to C) and comparative examples (ink liquids 101 and 102)
The following evaluation was performed about the ink-jet ink. The results are shown in Table 5. In Table 5,
"Color tone", "paper dependence", "waterfastness", "lightfastness",
"Wet heat storage property" and "ozone gas resistance" means that each ink for ink jet was converted to an ink jet printer (EPSON
Co., Ltd .; PM-700C) with photo glossy paper (EPS)
ON Company PM Photo Paper <Glossy> (KA420PSK, EPS
(ON) after the image was recorded.

<Color Tone> The reflection spectrum of the image formed on the photo glossy paper was measured at intervals of 10 nm in the 390-730 nm region, and this was measured as CIE L * a * b.
* A * and b * were calculated based on the color space system. JNC
The preferred color tone for cyan compared to the standard cyan color sample of JAPAN Color was defined as follows.

Preferred a *: -35.9 or more and 0 or less, Preferred b *: -50.4 or more and 0 or less ：: A preferred area for both a * and b * Δ: A preferred area for only one of a * and b * Both a * and b * are outside the preferred range

<Paper Dependency> The color tone between the image formed on the photo glossy paper and the image separately formed on plain paper for PPC is compared. The case where the difference between the images was large was evaluated as B (poor) and evaluated in two steps.

<Water resistance> The photo glossy paper on which the image was formed was dried for 1 hour at room temperature, immersed in deionized water for 10 seconds, allowed to dry naturally at room temperature, and observed for bleeding. A sample without bleeding was evaluated as A, a sample with slight bleeding as B, and a sample with much bleeding as C.

<Lightfastness> Xenon light (85000 lx) was irradiated on the photo glossy paper on which the image was formed using a weather meter (Atlas CI65) for 7 days, and the image density before and after the xenon irradiation was measured using a reflection densitometer. (X-Rite31
0TR) and evaluated as the residual dye ratio.
The reflection density was measured at three points of 1, 1.5 and 2.0. At any concentration, the residual dye ratio of 70% or more was A, and 1 or 2 points were less than 70% B, and the concentration was 7 at all concentrations.
The case of less than 0% was evaluated as C in three steps.

<Dark Heat Preservation> A sample of the photo glossy paper on which the image was formed was stored at 80 ° C. and 15% RH for 7 days, and the image density before and after the storage was measured using a reflection densitometer (X-Rite3).
10TR) and evaluated as the residual dye ratio. Regarding the dye remaining rate, the reflection density was 1, 1.5, 2
The evaluation was performed at points, and the results were evaluated as A when the residual ratio of the dye was 90% or more at any concentration, B when the percentage of the dyes was less than 90%, and C when the percentage was less than 90% at all concentrations.

<Ozone resistance> The photo glossy paper on which the image was formed was left in a box set at an ozone gas concentration of 0.5 ± 0.1 ppm, at room temperature and in a dark place for 7 days. Image density is measured with a reflection densitometer (X-Rite3)
10TR) and evaluated as the residual dye ratio. The reflection density is 3, 1.5 and 2.0.
Measured in points. Ozone gas concentration in the box is APP
LICS ozone gas monitor (Model: OZG-EM
-01). In any of the concentrations, the case where the residual ratio of the dye was 70% or more was evaluated as A, and B was evaluated when one or two points were less than 70%, and C was evaluated when it was less than 70% at all concentrations.

The value of the oxidation potential in Table 5 is 0.1 moldm
^In dimethylformamide containing tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the dye is 0.3%).
001 moldm ^-3 ) indicates the value of the oxidation potential of the dye (vs SCE) measured by DC polarography.

[0232]

[Table 5]

[0233]

Embedded image

As is clear from Table 5, the ink-jet ink of the present invention was excellent in color tone, small in dependence on paper, and excellent in water resistance, light resistance and ozone resistance. In particular, it is clear that the image storage stability such as light resistance and ozone resistance is excellent.

Example 2 Using the same cartridge manufactured in Example 1, an image was printed on an inkjet paper photo glossy paper EX manufactured by Fuji Photo Film using the same machine in Example 1, and the same evaluation as in Example 1 was performed. The same result as in Example 1 was obtained.

Example 3 The same ink prepared in Example 1 was packed in a cartridge of an ink jet printer BJ-F850 (manufactured by CANON), and an image was printed on the photo glossy paper GP-301 of the same company by the same machine. When the same evaluation as that of Example 1 was performed, the same result as that of Example 1 was obtained.

Example 4 (Preparation of Ink Liquid D)
7.04 g of sodium dioctylsulfosuccinate was combined with 4.22 g of the following high-boiling organic solvent (s-2), 5.63 g of the following high-boiling organic solvent (s-11), and 50 ml of ethyl acetate.
At 70 ° C. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse particle dispersion is used as a microfluidizer (MICROFL).
(UIDEX INC) to pass through at a pressure of 600 bar five times to obtain fine particles. The solvent was removed from the resulting emulsion using a rotary evaporator until the odor of ethyl acetate disappeared. Diethylene glycol 140 was added to the fine emulsion of the hydrophobic dye thus obtained.
g, glycerin 50g, SURFYNOL465 (Ai
An ink liquid D was prepared by adding 7 g of rProducts & Chemicals and 900 ml of deionized water.

[0238]

Embedded image

(Preparation of Ink Liquid E) An ink liquid E was prepared in the same manner as the ink liquid D, except that the dye 118 of the present invention in the ink liquid D was changed to the dye shown in the following Table 6 in an equimolar amount.

(Image Recording and Evaluation) The following evaluations were performed on the ink liquids D and E and the comparative ink liquids 101 and 102. The results are shown in Table 6 below. In Table 6,
"Color tone", "paper dependence", "waterfastness", "lightfastness",
"Dark heat preservation", "ozone gas resistance", and "oxidation potential"
Are the same as those described in the first embodiment.

[0241]

[Table 6]

As is clear from Table 6, the ink-jet ink of the present invention was excellent in color developability and color tone, had little dependence on paper, and was excellent in water resistance and light resistance.

Example 5 Using the same cartridge manufactured in Example 4, an image was printed on inkjet paper photo glossy paper EX manufactured by Fuji Photo Film using the same machine in Example 4, and the same evaluation as in Example 4 was performed. The same result as in Example 4 was obtained.

Example 6 The same ink produced in Example 4 was packed in a cartridge of an ink jet printer BJ-F850 (manufactured by CANON), and an image was printed on the photo glossy paper GP-301 by the same machine. When the same evaluation as that of Example 4 was performed, the same result as that of Example 4 was obtained.

[0245]

According to the present invention, 1) it has absorption characteristics excellent in color reproducibility as three primary color dyes, and has sufficient fastness to light, heat, humidity and active gas in the environment. Ink composition for printing such as ink jet, ink sheet for thermal transfer type image forming material, toner for electrophotography, which provides novel phthalocyanine dyes and 2) gives colored images and coloring materials with excellent hue and fastness , LCD and CCD
Provide various coloring compositions such as coloring compositions for color filters used in, dyeing solutions for dyeing various fibers,
3) In particular, there is provided an ink jet recording ink and an ink jet recording method which have a good hue by using the phthalocyanine dye and can form an image having high fastness to light and an active gas in the environment, particularly ozone gas. Can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // C07D 487/22 B41J 3/04 101Y F term (reference) 2C056 FC01 2H086 BA55 BA60 4C050 PA13 4H025 AA55 AB02 AB05 AC07 4J039 BC60 BE01 BE02 EA16 EA34 GA24

Claims (7)

[Claims] 1. A method for improving ozone resistance of a colored image material, comprising using a phthalocyanine dye having an oxidation potential higher than 1.0 V (vs. SCE). 2. The phthalocyanine dye of the following general formula (I)
Characterized in that it is a phthalocyanine dye represented by
The method for improving ozone resistance according to claim 1. Embedded imageIn the formula (I), X₁, X_Two, X_ThreeAnd X_FourAre independent
In addition, -SO-Z₁, -SO_Two-Z₁, -SO_TwoNR₁R_TwoAlso
Represents a sulfo group. Where Z₁Is replaced or omitted
Substituted alkyl group, substituted or unsubstituted cycloalkyl
Group, substituted or unsubstituted alkenyl group, substituted or
Unsubstituted aralkyl group, substituted or unsubstituted aryl
Represents a substituted or unsubstituted heterocyclic group. R₁Is
Hydrogen atom, a substituted or unsubstituted alkyl group, substituted if
Or unsubstituted cycloalkyl group, substituted or unsubstituted
Alkenyl group, substituted or unsubstituted aralkyl group,
Substituted or unsubstituted aryl group, or substituted or unsubstituted
Represents a substituted heterocyclic group, _TwoIs substituted or unsubstituted
Alkyl group, substituted or unsubstituted cycloalkyl
Group, substituted or unsubstituted alkenyl group, substituted or
Unsubstituted aralkyl group, substituted or unsubstituted aryl
Represents a group or a substituted or unsubstituted heterocyclic group. Y
₁, Y_Two, Y_ThreeAnd Y_FourAre each independently a hydrogen atom,
Logen atom, alkyl group, cycloalkyl group, alkenyl
Group, aralkyl group, aryl group, heterocyclic group, cyano
Group, hydroxyl group, nitro group, amino group, alkyl group
Mino group, alkoxy group, aryloxy group, amide group,
Arylamino group, ureido group, sulfamoylamino
Group, alkylthio group, arylthio group, alkoxycal
Bonylamino group, sulfonamide group, carbamoyl group,
Alkoxycarbonyl group, heterocyclic oxy group, azo group,
Acyloxy group, carbamoyloxy group, silyloxy
Group, aryloxycarbonyl group, aryloxycal
Bonylamino group, imide group, heterocyclic thio group, phosphoryl
Group, acyl group, carboxyl group, or sulfo group
However, each may further have a substituent. a₁~
a_Four, B₁~ B_FourIs X₁~ X_FourAnd Y₁~ Y_FourPlace
Represents a radix, a₁~ A_FourAre each independently an integer from 0 to 4
, But not all become 0 at the same time. b₁~
b_FourEach independently represents an integer of 0 to 4; Note that a₁~
a_FourAnd b₁~ B_FourRepresents an integer of 2 or more;₁
~ X_FourAnd Y₁~ Y_FourAre the same or different
Is also good. M is a hydrogen atom, a metal element or its oxide, water
Oxide or halide. 3. The phthalocyanine represented by the general formula (I)
A phthalocyanine represented by the following general formula (II):
3. The method for improving ozone resistance according to claim 2, wherein the ozone is a dye. Embedded imageIn the formula (II), X₁₁, X₁₂, X₁₃And X₁₄Is German
On the other hand, -SO-Z₁₁, -SO_Two-Z₁₁, -SO_TwoNR₁₁R
₁₂Or a sulfo group. Z₁₁Is substituted or unsubstituted
Alkyl group, substituted or unsubstituted cycloalkyl
Group, substituted or unsubstituted alkenyl group, substituted or
Unsubstituted aralkyl group, substituted or unsubstituted aryl
Represents a group or a substituted or unsubstituted heterocyclic group. R
₁₁Is a hydrogen atom, a substituted or unsubstituted alkyl group,
Substituted or unsubstituted cycloalkyl group, substituted or unsubstituted
Substituted alkenyl group, substituted or unsubstituted aralkyl
Group, substituted or unsubstituted aryl group, or
Or an unsubstituted heterocyclic group,₁₂Is replaced or
Unsubstituted alkyl group, substituted or unsubstituted cycloal
Killed group, substituted or unsubstituted alkenyl group,
Or unsubstituted aralkyl group, substituted or unsubstituted ant
A substituted or unsubstituted heterocyclic group.
You. Y₁₁, Y₁₂, Y₁₃, Y₁₄, Y₁₅, Y₁₆, Y₁₇and
Y₁₈Are each independently a hydrogen atom, a halogen atom,
Kill group, cycloalkyl group, alkenyl group, aralkyl
Group, aryl group, heterocyclic group, cyano group, hydroxyl
Group, nitro group, amino group, alkylamino group, alkoxy
Group, aryloxy group, amide group, arylamino
Group, ureido group, sulfamoylamino group, alkylthio
O group, arylthio group, alkoxycarbonylamino
Group, sulfonamide group, carbamoyl group, alkoxyca
Rubonyl group, heterocyclic oxy group, azo group, acyloxy
Group, carbamoyloxy group, silyloxy group, aryl
Oxycarbonyl group, aryloxycarbonylamino
Group, imide group, heterocyclic thio group, phosphoryl group, acyl
Group, carboxyl group, or sulfo group.
They may further have a substituent. a₁₁~ A₁₄Are each
X₁₁~ X₁₄And independently represents 0 to 2
Represents an integer, but not all at the same time. What
Oh, a₁₁~ A ₁₄Represents two, two X's₁₁~ X₁₄Haso
They may be the same or different. M is a hydrogen atom, gold
Group element or its oxide, hydroxide or halogenated
Things. 4. The phthalocyanine dye represented by the general formula (I) or (II), wherein the phthalocyanine dye has at least four ionic hydrophilic groups in one molecule (where the ion The hydrophilic group represents a carboxyl group, a sulfo group or a quaternary ammonium group, and may be the same or different.)
The method for improving ozone resistance according to claim 2 or 3, wherein: 5. The phthalocyanine represented by the general formula (I)
A phthalocyanine represented by the following general formula (III),
3. The method for improving ozone resistance according to claim 2, which is a nin dye. Embedded imageIn the formula (III), X_{twenty one}, X_{twenty two}, X_{twenty three}And X_{twenty four}Are each
Independently, -SO-Z_{twenty one}, -SO_Two-Z_{twenty one}, -SO_TwoNR_{twenty one}
R_{twenty two}Or a sulfo group. Z_{twenty one}Is replaced or omitted
Substituted alkyl group, substituted or unsubstituted cycloalkyl
Group, substituted or unsubstituted alkenyl group, substituted or
Unsubstituted aralkyl group, substituted or unsubstituted aryl
Represents a group or a substituted or unsubstituted heterocyclic group. R
_{twenty one}Is a hydrogen atom, a substituted or unsubstituted alkyl group,
Substituted or unsubstituted cycloalkyl group, substituted or unsubstituted
Substituted alkenyl group, substituted or unsubstituted aralkyl
Group, substituted or unsubstituted aryl group, or
Or an unsubstituted heterocyclic group,_{twenty two}Is replaced or
Unsubstituted alkyl group, substituted or unsubstituted cycloal
Killed group, substituted or unsubstituted alkenyl group,
Or unsubstituted aralkyl group, substituted or unsubstituted ant
A substituted or unsubstituted heterocyclic group.
You. a_{twenty one}~ A_{twenty four}Is X_{twenty one}~ X_{twenty four}The number of substituents of
And each independently represents an integer of 0 to 2;
Sometimes it does not go to zero. Note that a_{twenty one}~ A _{twenty four}Represents 2.
Sometimes two X_{twenty one}~ X_{twenty four}Are the same or different
May be. M is a hydrogen atom, a metal element or an oxide thereof,
Hydroxide or halide. 6. A method for improving ozone resistance of a colored image material, comprising using the ink composition for inkjet recording containing the phthalocyanine dye according to any one of claims 1 to 5. 7. An ink jet recording method comprising forming an image on an image receiving material having an ink image receiving layer containing white inorganic pigment particles on a support using the ink composition for ink jet recording according to claim 6. Recording method.