JP2002309118A - Colored composition containing phthalocyanine compound, ink for ink jet recording, ink jet recording method, and method for improving resistance to fading due to ozone gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new phthalocyanine compound, an ink used for ink jet recording and giving an image excellent in color hue and having high fastnesses to light and ozone gas, an ink jet recording method, colored compositions used for an ink sheet for thermal recording, a color toner for electrophotography and a color filter for an image pickup device, and a method for enhancing the resistance of an image to an oxidizing environment such as an atmosphere of ozone. SOLUTION: The phthalocyanine compound is represented by general formula 1 (wherein R1 to R8 are each H, halogen or the like; and W1 to W4 are each any one of R1 to R8 , or a sulfonylsulfamoyl group, or an acylsulfamoyl group, provided that one or more of W1 to W4 comprise groups having both an electron attracting group with a Hammett substituent constant of 0.20 or higher and one or more ionic hydrophilic groups) and has an association material absorption stronger than a monomer absorption on the spectral absorption curve. The colored compositions contain the phthalocyanine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition containing a phthalocyanine compound, in particular, a water-soluble ink for cyan ink jet recording, an ink jet recording method, and a method for improving ozone gas fading resistance of an image recorded matter by utilizing 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 recording material, and an electrophotographic recording material have been used. Materials, transfer-type silver halide photosensitive materials, printing inks, recording pens, and the like are actively used. Further, a color filter is used for recording and reproducing a color image in an image pickup device such as a CCD in a photographing device, and in an LCD or a PDP in a display in a display. 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 to reproduce or record a full-color image. The fact is that there is no robust dye that has absorption characteristics capable of realizing the above and can withstand various use conditions and environmental conditions, and improvement is strongly desired.

[0003] The ink jet recording method is rapidly spreading and developing due to its low material cost, high speed recording, low noise during recording, and easy color recording. is there. 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 response to an image information signal. , A method in which bubbles are generated in ink by heat to discharge droplets, a method using ultrasonic waves, and a method in which droplets are sucked and discharged by electrostatic force. Further, as the ink-jet ink, a water-based ink, an oil-based ink, or a solid (melt-type) ink is used.

[0004] Dyes used in such ink-jet inks have good solubility or dispersibility in solvents, high density recording is possible, good hue, light, heat, Activated gas in the environment (NO
x, ozone and other oxidizing gases, SOx, etc.), excellent resistance to water and chemicals, good fixability to the image receiving material, low bleeding, storage as ink It is required to have excellent properties, no toxicity, high purity, and to be available at low cost.

[0005] In particular, a dye having a good cyan hue and being fast to light, humidity, and heat, in particular, printing on an image receiving material having an ink receiving layer containing porous white inorganic pigment particles. In some cases, it is strongly desired to be robust against oxidizing gases such as ozone in the environment.

In a color copier or a color laser printer using an electrophotographic system, a toner in which a colorant is dispersed in resin particles is generally widely used. As the performance required for the color toner, an absorption characteristic capable of realizing a preferable color reproduction range, particularly, Overhead Pro
high transparency (transparency), which is a problem when used in a JET (hereinafter referred to as OHP), and various fastnesses under the environmental conditions used. JP-A-62-157051 discloses a toner in which a pigment is dispersed as particles as a colorant.
Although these toners are disclosed in JP-A-62-255556 and JP-A-6-118715, these toners are excellent in light fastness, but are insoluble and easily aggregated, resulting in a decrease in transparency of the colored layer and a hue of transmitted color. Change is a problem. On the other hand, a toner using a dye as a coloring material is disclosed in Japanese Patent Laid-Open No. 3-276161.
Nos. 7,209,912 and 8,123,085, these toners have high transparency,
Although there is no hue change, there is a problem in light fastness.

[0007] Thermal transfer recording has the advantages that the size of the apparatus can be reduced, the cost can be reduced, the operation and maintenance are easy, and the running cost is low. The performance required for dyes used in thermal transfer recording is absorption characteristics that can achieve a favorable color reproduction range, compatibility between thermal transferability and fixability after transfer, thermal stability, and various robustness of the obtained image. However, none of the conventionally known dyes satisfy all of these properties. For example, for the purpose of improving fixability and light resistance, a heat-sensitive transfer recording material and an image forming method in which a heat-diffusible dye is chelated by a transition metal ion previously added to an image-receiving material are disclosed in JP-A-60-239.
No. 8, etc., the absorption characteristics of the formed chelate dye are at an unsatisfactory level, and there are also environmental problems due to the use of transition metals.

Since a color filter is required to have high transparency, a method called a dyeing method of coloring with a dye has been performed. For example, a color filter can be manufactured by sequentially forming a pattern by exposing and developing a photoresist to be dyed by pattern exposure and then dyeing it with a filter color dye for all filter colors. U.S. Pat.
A color filter can also be produced by a method using a positive resist described in JP-A-8-501 and JP-A-6-35182. These methods have high transmittance due to the use of dyes, and have excellent optical properties of color filters, but have limitations in light resistance and heat resistance, and are excellent in various resistances.
A highly transparent dye has been desired. On the other hand, a method of using an organic pigment having excellent light resistance and heat resistance in place of a dye is widely known, but it has been difficult to obtain optical properties like a dye with a color filter using a pigment.

Dyes used in the above-mentioned applications are required to have the following properties in common. That is, it has favorable absorption characteristics in terms of color reproducibility, and robustness under the used environmental conditions, for example, light resistance, heat resistance, moisture resistance, resistance to oxidizing gases such as ozone, and other chemicals such as sulfur dioxide. Good absorption properties, large molar absorption coefficient, and the like.

Hitherto, a phthalocyanine compound excellent in hue and light fastness has been used as a cyan dye in most cases, but does not have sufficient fastness to an oxidizing gas, particularly ozone. Therefore, improvement is desired.

The structure of phthalocyanine and triphenylmethane is typical of the cyan dye skeleton used in the ink for ink jet.

The most widely reported and utilized representative phthalocyanine compounds include the following phthalocyanine derivatives.

[0013] Direct Blue 86 or Di
copper phthalocyanine compound such as Rect Blue 199 [for example, Cu—Pc— (SO ₃ Na) _m : m = 1 to 4
(Pc means phthalocyanine skeleton).

JP-A-62-190273, JP-A-62-190273
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 reagents described in JP-A-3-37176, JP-A-63-304071, JP-A-5-171850, WO 00/08102 [for example, Cu-Pc- (C
O ₂ H) _m (CONR ₁ R ₂ ) _n : m + n = 0 to 4]

Japanese Patent Application Laid-Open No. Sho 59-30874,
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. No. 6,086,955, WO 99
/ 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]

By the way, Direct Blue 86 or Direct BL which is widely used at present is generally used.
The phthalocyanine dye represented by ue 199 has a feature that it is superior in light fastness to generally known magenta dyes and yellow dyes.

However, phthalocyanine dyes have a green hue under acidic conditions and are unsuitable for cyan ink. 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, triphenylmethane dye (or pigment)
Is good in hue, but very poor in light resistance, ozone gas resistance 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. Dyestuffs and ink compositions having excellent robustness and robustness to active gases in the environment (oxidizing gases such as NOx and ozone as well as SOx) have been increasingly desired.

However, the development of cyan dyes (for example, phthalocyanine dyes) and cyan inks that satisfy these requirements at a high level is accompanied by difficulties, and there are still no dyes and inks that satisfy the requirements. It is in.

Hitherto, as a phthalocyanine dye imparted with ozone gas fading resistance, JP-A-3-103484 has been used.
JP-A-4-39365, JP-A-2000-3030
No. 09, etc. are disclosed, but none of them have achieved a balance between hue and fastness to light and oxidizing gas. A cyan ink product which still sufficiently satisfies the market demands has been developed. Not yet available.

[0026]

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, an object of the present invention is to provide (1) a novel dye having excellent absorption characteristics as a color pigment having excellent color reproducibility and having sufficient fastness to light, heat, humidity and an active gas in the environment. Providing a colored composition; (2) having, in particular, the properties described in (1) above, and printing inks such as ink jets, ink sheets for thermosensitive recording materials, color toners for electrophotography, LCDs To provide various coloring compositions such as color filters used in displays such as PDPs and imaging devices such as CCDs. (3) Particularly, the use of the phthalocyanine compound derivative has a favorable hue, and is effective in light and environmental conditions. And (4) providing an inkjet ink and an inkjet recording method capable of forming an image having high robustness to an active gas, particularly an ozone gas. By utilizing jet recording method, and an object thereof is to provide an image robust method for improving ozone gas discoloration resistance of an image recorded material.

[0027]

The present inventors have studied in detail a phthalocyanine derivative having good hue, high light fastness and high gas fastness (particularly, ozone gas). The following general formula (I) having specific absorption characteristics, (2) specific oxidation potential, and (3) specific dye structure (specific substituent type is introduced into specific substitution position at specific substitution number).
In particular, they have found that the above problem can be solved by a phthalocyanine compound represented by the general formula (II), especially the general formula (III), and have completed the present invention based on this novel finding. That is, the above object of the present invention is achieved by the following means.

1. 660 in the spectral absorption curve of the aqueous solution
maximum absorbance b in the absorption band from nm to 680 nm,
Coloring characterized by having an absorbance ratio b / a to the maximum absorbance a in the absorption band from 600 nm to 640 nm of less than 1, and containing a water-soluble phthalocyanine compound represented by the following general formula (I). Composition.

[0029]

Embedded image

In the general formula (I), R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom,
Halogen atom, alkyl 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, aryl Amino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group A carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, or an acyl group, each of which may further have a substituent. Good. W ₁ , W ₂ , W ₃ , and W ₄ are each independently a group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ or a sulfonyl sulfone; Represents a famoyl group or an acylsulfamoyl group, each of which may further have a substituent. However, W ₁ , W ₂ ,
At least one of W ₃ and W ₄ is a Hammett's substituent constant σ
a p-value of 0.20 or more is an electron-withdrawing group, and
At least one of W ₁ , W ₂ , W ₃ and W ₄ is itself an ionic hydrophilic group or has an ionic hydrophilic group as a substituent. l, m, n, and p represent an integer of 1 or 2. M is a hydrogen atom, a metal element or an oxide thereof,
Represents hydroxide or halide.

2. The colored composition according to claim 1, wherein the phthalocyanine compound represented by the general formula (I) is a phthalocyanine compound having an oxidation potential nobleer than 1.0 eV (vsSCE).

3. 3. The colored composition according to the above 1 or 2, wherein the phthalocyanine compound represented by the general formula (I) is a phthalocyanine compound represented by the following general formula (II).

[0033]

Embedded image

In the general formula (II), W ₁ , W ₂ , W ₃ and W ₄ are
Hammett's substituent constant σp value is independently 0.20
It represents the above electron-withdrawing group. _{However, W 1, W 2, W} 3, W 4
Is an ionic hydrophilic group itself or has an ionic hydrophilic group as a substituent.
l, m, n, p and M have the same meanings as l, m, n, p and M in the general formula (I), respectively.

4. 4. The coloring composition according to any one of the above items 1 to 3, wherein the phthalocyanine compound represented by the general formula (II) is a phthalocyanine compound represented by the following general formula (III).

[0036]

Embedded image

In the general formula (III), W ₁ , W ₂ , W ₃ , W
₄ is each independently -SO-Z and / or -SO ₂
-Z and / or -SO ₂ NY ₁ Y ₂ and / or -SO ₂
Represents a NY ₃ SO ₂ Y _2, and / or -SO ₂ NY ₃ COY _2. Z is each independently 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 group; Represents a heterocyclic group. Y ₁ is each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group Represents a substituted or unsubstituted heterocyclic group, and Y ₂ is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group,
Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Y ₃ is each independently a hydrogen atom, lithium, sodium, potassium, a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. l, m, n, p and M are
Each has the same meaning as l, m, n, p and M in the general formula (II). However, the phthalocyanine compound represented by the general formula (III) has at least four or more ionic hydrophilic groups in one molecule.

5. The water-soluble phthalocyanine compound has a maximum absorbance b in an absorption band from 660 nm to 680 nm in a spectral absorption curve of an aqueous solution, and a maximum absorbance b in a range from 600 nm to 640 nm.
Absorbance ratio b / a with maximum absorbance a in the absorption band up to nm
Is less than 0.8 and is a water-soluble phthalocyanine compound represented by the general formula (III).

6. The coloring composition according to the above item 4 or 5, wherein the phthalocyanine compound represented by the general formula (III) is a phthalocyanine compound whose oxidation potential is nobler than 1.1 eV (vsSCE). .

7. 7. An ink-jet ink comprising the coloring composition according to any one of the above items 1 to 6.

8. In the phthalocyanine compound represented by the general formula (III), the ionic hydrophilic group is a group selected from a carboxyl group, a sulfo group, a quaternary ammonium group, a sulfonylsulfamoyl group, and an acylsulfamoyl group. 8. The ink-jet ink according to the item 7, wherein

9. 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-jet ink described in 7 or 8 above.

10. 9. A method for improving ozone gas discoloration resistance of an image recorded matter, wherein an image is formed using the inkjet ink according to any one of the above items 7 and 8.

[0044]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The coloring composition in the present invention means a composition containing a coloring material such as a dye or a pigment and can be suitably used particularly for image formation.

[Phthalocyanine compound] The phthalocyanine compound used in the present invention has the maximum absorbance b in the absorption band from 660 nm to 680 nm and the maximum absorbance a in the absorption band from 600 nm to 640 nm in the spectral absorption curve of the aqueous solution. A water-soluble phthalocyanine compound having a ratio b / a of less than 1 and represented by the general formula (I). In the present specification, the absorbance ratio refers to an absorbance ratio obtained under the following conditions. That is, JIS Z812
The measurement temperature is selected from the range of 15 to 30 ° C. by a spectrophotometer based on the definition of 0-86, the measurement cell length is set to 10 mm, the phthalocyanine compound of the present invention is weighed in a fixed amount (converted to molecular weight), and distilled. After dilution with water, within the target absorbance (any one of absorbance a and absorbance b is 0.8 to 1.0
To obtain a spectral absorption curve.
The ratio b / a between the maximum absorbance b in the absorption band from 660 nm to 680 nm and the maximum absorbance a in the absorption band from 600 nm to 640 nm in the obtained spectral absorption curve is defined as the absorbance ratio.

FIG. 1 is an explanatory diagram showing how to determine the above-mentioned absorbance ratio. In FIG. 1, the vertical axis indicates absorbance (ABS), and the horizontal axis indicates wavelength (nm). The spectral absorption curve of the aqueous solution of the phthalocyanine compound shown in FIG. 1 is from 660 nm to 680 under the conditions of the above-mentioned spectrophotometer, measuring cell length and pH.
It is measured by diluting with distilled water so that the maximum absorbance b at nm becomes 1.0 (0.8 to 1.0 is sufficient). At this time, the maximum absorbance a at 600 nm to 640 nm is read. The absorbance ratio b / a under the conditions specified in the present invention can be easily obtained. The distilled water used for preparing and diluting the aqueous solution is distilled water having a pH of 5 to 8.

A water-soluble phthalocyanine compound having a value of the absorbance ratio b / a of less than 1 has good characteristics of fastness (particularly light fastness and ozone gas fastness) of a formed image as a colorant. However, the value of the absorbance ratio b / a is 0.8
Is preferably less than 0.6, and particularly preferably 0.6 or less.

In the present invention, the oxidation potential is 1.0 V (vs. SC
A water-soluble phthalocyanine compound represented by the general formula (I) which is more noble than E) 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 whose oxidation potential is more noble than 1.2 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 Methods in Ele" by Delahay
ctrochemistry ”(1954, Interscience Publishe
rs company) and A. J. Bard et al., “Electrochemical Me
thods "(1980, published by John Wiley & Sons) and" Electrochemical Measurement "by Akira Fujishima et al. (1984, published by Gihodo Shuppan).

[0050] 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 ^- Dissolve ⁶ mol / liter and use cyclic voltammetry or DC polarography equipment to sweep the oxidation wave generated when carbon (GC) is swept to the oxidation side (noble side) using a rotating platinum electrode as a working electrode and a rotating platinum electrode as a counter electrode. Approximate by a straight line, a line segment formed by the intersection of this straight line and the residual current / potential straight line, and the intersection of the straight line and the saturated current straight line (or the intersection of the straight line parallel to the vertical axis passing the peak potential value) The intermediate potential value of SCE
(Saturated calomel electrode). 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). The supporting electrolyte and the solvent used are
An appropriate one can be selected depending on the oxidation potential and solubility of the test sample. The supporting electrolytes and solvents that can be used are described in Akira Fujishima et al., "Electrochemical Measurement Method" (1984, published by Gihodo Shuppan Co., Ltd.), pp. 101-118. In addition, in the concentration range of the above-mentioned measurement solvent and the phthalocyanine compound sample, the oxidation potential in a non-associated state is measured.

The value of Eox indicates the ease with which electrons move 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, if the Hammett's substituent constant σp value, which is a measure of the electron withdrawing or electron donating property of the substituent, is used, substitution having a large σp value such as a sulfinyl group, a sulfonyl group, a sulfamoyl group, and a sulfonylsulfamoyl group is possible. It can be said that by introducing a group, the oxidation potential can be made more noble.

Here, the Hammett's substituent constant σp value used in the present specification will be described briefly. Hammett's rule was used by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
Empirical rule, which is widely accepted today. The substituent constants determined by Hammett's rule include σp values and σm values, and these values can be found in many general books. For example, JADean
Hen, "Lange's Handbook of Chemistry", 12th edition, 1
979 (Mc Graw-Hill) and extra edition of "Chemical Field", 1
22, No. 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to the substituent having a value known in the literature, which can be found in the above-mentioned book. However, it is needless to say that even if the value is unknown in the literature, it also includes a substituent that would be included in the range when measured based on the Hammett rule. Although the compound represented by the general formula (I), (II) or (III) of the present invention is not a benzene derivative, the σp value is used as a measure of the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense in the future.

Next, the phthalocyanine compound represented by formula (I) of the present invention will be described in detail.

[0054]

Embedded image

In the general formula (I), R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently
Hydrogen atom, halogen atom, alkyl 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 group, arylthio group,
Alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group,
Represents an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, or an acyl 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,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group and sulfinyl group are preferred, especially hydrogen atom,
A halogen atom and a cyano group are preferred, and a hydrogen atom is most preferred.

W ₁ , W ₂ , W ₃ and W ₄ are each independently
Halogen atom, alkyl 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, aryl Amino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group A carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a sulfonylsulfamoyl group, an acylflufamoyl group, a phosphoryl group, or It represents a group, each of which may further have a substituent.

In the general formula (I), W ₁ , W ₂ ,
At least one of the groups represented by W ₃ and W ₄ is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Preferably, it is 0.30 or more electron-withdrawing group. The upper limit is an electron-withdrawing group having a σp value of 1.0 or less.

Specific examples of W ₁ , W ₂ , W ₃ , and W ₄ which are electron-withdrawing groups having a σp value of 0.20 or more include acyl, acyloxy, carbamoyl, alkyloxycarbonyl, aryloxy Carbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group,
Diarylphosphinyl group, alkylsulfinyl group,
Arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonyloxy, acylthio, sulfamoyl, thiocyanate, thiocarbonyl, halogenated alkyl, halogenated alkoxy, halogenated aryloxy, halogenated alkylamino , A halogenated alkylthio group, σp value of 0.2
Examples include an aryl group, a heterocyclic group, a halogen atom, an azo group, or a selenocyanate group substituted with 0 or more other electron-withdrawing groups.

Preferred examples of W ₁ , W ₂ , W ₃ and W ₄ include an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and a carbamoyl group having 2 to 1 carbon atoms.
2, an alkyloxycarbonyl group having 2 to 18 carbon atoms, an aryloxycarbonyl group having 7 to 18 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, and 6 to 18 carbon atoms
Arylsulfinyl group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, a sulfamoyl group having 0 to 12 carbon atoms,
2, a halogenated alkyloxy group having 1 to 12 carbon atoms, a halogenated alkylthio group having 1 to 12 carbon atoms, a halogenated aryloxy group having 7 to 18 carbon atoms, two or more σp 0.20 or more And an aryl group having 7 to 18 carbon atoms and a 5- to 8-membered heterocyclic group having a nitrogen atom, an oxygen atom or a sulfur atom and having 1 to 18 carbon atoms, which are substituted with another electron-withdrawing group. Can be.

More preferred are an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, and a sulfamoyl group having 0 to 12 carbon atoms.

Particularly preferred W ₁ , W ₂ , W ₃ and W ₄ are an alkylsulfonyl group having 1 to 12 carbon atoms and a sulfamoyl group having 0 to 12 carbon atoms, and most preferred are those having 1 to 12 carbon atoms. It is an alkylsulfonyl group.

Of these, a halogen atom, an aryl group, a cyano group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a sulfinyl group, a sulfonylsulfamoyl group, an acylflufamoyl group, a phosphoryl group, and an acyl group are preferred. In particular, a sulfamoyl group, a sulfonyl group, a sulfinyl group, a sulfonylsulfamoyl group, an acylflufamoyl group, a phosphoryl group, and an acyl group are preferable, and among them, a sulfamoyl group, a sulfonyl group, a sulfonylsulfamoyl group, and an acylflufamoyl group are preferable. Groups are particularly preferred, and sulfamoyl and sulfonyl groups are most preferred.

At least one of the groups represented by W ₁ , W ₂ , W ₃ and W ₄ is itself an ionic hydrophilic group or has an ionic hydrophilic group as a substituent.

The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, and a quaternary ammonium group,
And a sulfonylsulfamoyl group and an acylsulfamoyl group. As the ionic hydrophilic group, a carboxyl group, a sulfo group and a sulfonylsulfamoyl group are preferable, and a sulfo group is particularly preferable. The carboxyl group, sulfo group, sulfonylsulfamoyl group and acylsulfamoyl group may be in the form of a salt, and examples of the counter ion forming a salt include alkali metal ions (eg,
Sodium ions, potassium ions) and organic cations (eg, tetramethylguanidinium ion).

L, m, n and p are each independently preferably an integer of 1 or 2 satisfying 4 ≦ l + m + n + p ≦ 8, more preferably satisfying 4 ≦ l + m + n + p ≦ 6, and most preferably each is 1 (l = M = n = p = 1).

M is a hydrogen atom, a metal element, a metal oxide,
Represents metal hydroxide or metal halide. Desirable M is, besides a hydrogen atom, a metal element 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 metal oxide include VO and GeO. The metal hydroxides include Si (OH) ₂ , Cr (O
H) ₂ , Sn (OH) _{2 and the} like. Further, as metal halides, AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeC
l, GaCl, ZrCl and the like. Especially, Cu, N
i, Zn, Al, etc. are preferred, and Cu is most preferred.

In the phthalocyanine compound represented by the general formula (I), Pc (phthalocyanine ring) is a dimer (for example, Pc-M-L-M-
Pc) or a trimer may be formed, in which case a plurality of M 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 -, imino group -NH-, a methylene group -CH ₂
-, And groups formed by combining these are preferred.

The above substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
The groups in which R ₆ , R ₇ , R ₈ and W ₁ , W ₂ , W ₃ , W ₄ can further have a substituent may further have the following substituents.

A halogen atom (for example, a chlorine atom or a bromine atom), a linear or branched alkyl group having 1 to 12 carbon atoms,
An aralkyl group having 7 to 18 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a linear or branched alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group which may have a side chain having 3 to 12 carbon atoms, A cycloalkenyl group having 3 to 12 carbon atoms which may have a side chain; specifically, an alkyl group (eg, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoro Each group such as methyl and cyclopentyl), an aryl group (for example, phenyl, 4-t-butylphenyl,
Each group such as 4-di-t-amylphenyl), a heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl,
Each group such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy) , 2-methanesulfonylethoxy, etc.), an aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy,
Each group such as 3-methoxycarbamoyl),

An acylamino group (for example, acetamido,
Groups such as benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), an alkylamino group (eg, each group such as methylamino, butylamino, diethylamino, methylbutylamino), an anilino group (eg, Phenylamino, 2-chloroanilino, etc.), ureido groups (eg, phenylureido, methylureide, N, N-dibutylureide, etc.),
Sulfamoylamino group (for example, N, N-dipropylsulfamoylamino group), alkylthio group (for example,
Groups such as methylthio, octylthio, 2-phenoxyethylthio), and arylthio groups (for example, phenylthio, 2-butoxy-5-t-octylphenylthio,
-Carboxyphenylthio and the like), alkyloxycarbonylamino group (for example, methoxycarbonylamino group), sulfonamide group (for example, each group such as methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), carbamoyl Groups (eg, N-
Groups such as ethylcarbamoyl and N, N-dibutylcarbamoyl), and sulfamoyl groups (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl,
Groups such as N, N-diethylsulfamoyl), sulfonyl groups (eg, groups such as methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), and alkyloxycarbonyl groups (eg, methoxycarbonyl, butyloxycarbonyl, etc.) Each group),

A heterocyclic oxy group (for example, each group such as 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy), an azo group (for example, phenylazo,
Groups such as 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), an acyloxy group (eg, an acetoxy group), a carbamoyloxy group (eg, N-methylcarbamoyl) Oxy, N-phenylcarbamoyloxy, etc.), silyloxy groups (eg, trimethylsilyloxy, dibutylmethylsilyloxy, etc.),
Aryloxycarbonylamino group (for example, phenoxycarbonylamino group), imide group (for example, each group such as N-succinimide, N-phthalimime), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4- Di-phenoxy-1,3,5-triazole-6-thio,
Groups such as 2-pyridylthio), a sulfinyl group (eg, a 3-phenoxypropylsulfinyl group), a phosphonyl group (eg, a group such as phenoxyphosphonyl, octyloxyphosphonyl, and phenylphosphonyl), and an aryloxycarbonyl group ( For example, a phenoxycarbonyl group), an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, etc.), an ionic hydrophilic group (eg, carboxyl group, sulfo group, quaternary ammonium group, sulfonyl sulfamoyl) Group and acylsulfamoyl group); and other examples include a cyano group, a hydroxyl group, a nitro group, a carboxyl group, and an amino group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And halogen atoms represented by W ₁ , W ₂ , W ₃ and W ₄ include:
Examples include a fluorine atom, a chlorine atom and a bromine atom.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the alkyl groups represented by W ₁ , W ₂ , W ₃ , and W ₄ include an alkyl group having a substituent and an unsubstituted alkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms excluding a substituent is preferable. 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,
Groups such as cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl are included.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the cycloalkyl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include:
It includes a substituted cycloalkyl group and an unsubstituted cycloalkyl group. As the cycloalkyl group, a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
The alkenyl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include alkenyl groups having a substituent and unsubstituted alkenyl groups. As the alkenyl group, an alkenyl group having 2 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group, an allyl group and the like.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And aralkyl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include:
An aralkyl group having a substituent and an unsubstituted aralkyl group are included. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
The aryl groups represented by W ₁ , W ₂ , W ₃ , and W ₄ include an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms when a substituent is removed is preferable. 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 groups such as phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And W _1, the W _2, W _3, W ₄ heterocyclic group represented, include a heterocyclic group and an unsubstituted heterocyclic group having a substituent. As the heterocyclic group, a 5- or 6-membered heterocyclic group is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group and a 2-furyl group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the alkylamino groups represented by W ₁ , W ₂ , W ₃ and W ₄ include:
It includes a substituted alkylamino group and an unsubstituted alkylamino group. As the alkylamino group, an alkylamino group having 1 to 6 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the alkoxy groups represented by W ₁ , W ₂ , W ₃ and W ₄ include an alkoxy group having a substituent and an unsubstituted alkoxy group. As the alkoxy group, an alkoxy group having from 1 to 12 carbon atoms excluding a substituent is preferable. 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.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the aryloxy groups represented by W ₁ , W ₂ , W ₃ and W ₄ include:
An aryloxy group having a substituent and an unsubstituted aryloxy group are included. As the aryloxy group, an aryloxy group having 6 to 12 carbon atoms when a substituent is removed is preferable. 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.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
The amide groups represented by W ₁ , W ₂ , W ₃ , and W ₄ include an amide group having a substituent and an unsubstituted amide group. The amide group has 2 carbon atoms when a substituent is removed.
-12 amide groups are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of amide groups include acetamido, propionamido, benzamido, and 3,
Includes a 5-disulfobenzamide group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the arylamino groups represented by W ₁ , W ₂ , W ₃ and W ₄ include:
An arylamino group having a substituent and an unsubstituted arylamino group are included. As the arylamino group, an arylamino group having 6 to 12 carbon atoms when a substituent is removed is preferable. 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.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the ureido groups represented by W ₁ , W ₂ , W ₃ and W ₄ include ureido groups having a substituent and unsubstituted ureido groups. As the ureido group, a ureido group having 1 to 12 carbon atoms when a substituent is removed is preferable. 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.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the sulfamoylamino groups represented by W ₁ , W ₂ , W ₃ and W ₄ include a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include an N, N-dipropylsulfamoylamino group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the alkylthio groups represented by W ₁ , W ₂ , W ₃ and W ₄ include an alkylthio group having a substituent and an unsubstituted alkylthio group. As the alkylthio group, an alkylthio group having from 1 to 12 carbon atoms excluding a substituent is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the arylthio groups represented by W ₁ , W ₂ , W ₃ , and W ₄ include an arylthio group having a substituent and an unsubstituted arylthio group. As the arylthio group, an arylthio group having from 6 to 12 carbon atoms when a substituent is excluded is preferable. 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.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the _{W 1, W 2, W 3} , W 4 alkoxycarbonylamino group represented by include alkoxycarbonylamino group and an unsubstituted alkoxycarbonylamino group having a substituent. As the alkoxycarbonylamino group, an alkoxycarbonylamino group having from 2 to 12 carbon atoms excluding a substituent is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the sulfonamide groups represented by W ₁ , W ₂ , W ₃ and W ₄ include:
It includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group. As the sulfonamide group, a sulfonamide group having from 1 to 12 carbon atoms excluding a substituent is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the carbamoyl groups represented by W ₁ , W ₂ , W ₃ , and W ₄ include 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.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the sulfamoyl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include:
It includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group,
An aryl group is included. Examples of the sulfamoyl group include a dimethylsulfamoyl group, a di- (2-hydroxyethyl) sulfamoyl group, and a phenylsulfamoyl group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the sulfonyl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include a sulfonyl group having a substituent and an unsubstituted sulfonyl group. Examples of the substituent include an alkyl group and an aryl group. Examples of the sulfonyl group include a methanesulfonyl group and a phenylsulfonyl group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the alkoxycarbonyl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the heterocyclic oxy groups represented by W ₁ , W ₂ , W ₃ and W ₄ include:
It includes a substituted heterocyclic oxy group and an unsubstituted heterocyclic oxy group. As the heterocyclic oxy group, 5
A heterocyclic oxy group having a 6-membered or 6-membered heterocyclic ring is preferred. Examples of the substituent include a hydroxyl group and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
The azo group represented by W ₁ , W ₂ , W ₃ , and W ₄ includes an azo group having a substituent and an unsubstituted azo group. Examples of the azo group include a p-nitrophenylazo group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the acyloxy groups represented by W ₁ , W ₂ , W ₃ and W ₄ include an acyloxy group having a substituent and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group.
Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the carbamoyloxy groups represented by W ₁ , W ₂ , W ₃ and W ₄ include a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of substituents include
Includes alkyl groups. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the silyloxy groups represented by W ₁ , W ₂ , W ₃ and W 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.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the aryloxycarbonyl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of aryloxycarbonyl groups include:
Includes phenoxycarbonyl groups.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the _{W 1, W 2, W 3} , W 4 aryloxycarbonylamino group represented by include aryloxycarbonylamino group and an unsubstituted aryloxycarbonylamino group having a substituent. The aryloxycarbonylamino group has from 7 to 1 carbon atoms when a substituent is excluded.
Two aryloxycarbonylamino groups are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the imide groups represented by W ₁ , W ₂ , W ₃ and W ₄ include imide groups having a substituent and unsubstituted imide groups. Examples of the imide group include an N-phthalimido group and an N-succinimido group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the heterocyclic thio groups represented by W ₁ , W ₂ , W ₃ and W ₄ include a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. The heterocyclic thio group preferably has a 5- or 6-membered hetero ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the sulfinyl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include a sulfinyl group having a substituent and an unsubstituted sulfinyl group. Examples of the substituent include an alkyl group and an aryl group.
A group. Examples of the sulfinyl group include a phenylsulfinyl group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
And the phosphoryl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include a phosphoryl group having a substituent and an unsubstituted phosphoryl group. Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
The acyl group represented by W ₁ , W ₂ , W ₃ , and W ₄ includes an acyl group having a substituent and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The sulfonylsulfamoyl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include a substituted sulfonylsulfamoyl group and an unsubstituted sulfonylsulfamoyl group. As the sulfonylsulfamoyl group, a sulfonylsulfamoyl group having 1 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonylsulfamoyl group include a methanesulfonylsulfamoyl group and a benzenesulfonylsulfamoyl group.

The acylsulfamoyl groups represented by W ₁ , W ₂ , W ₃ and W ₄ include an acylsulfamoyl group having a substituent and an unsubstituted acylsulfamoyl group. As the acylsulfamoyl group, an acylsulfamoyl group having 2 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group.
Examples of the acylsulfamoyl group include an acetylsulfamoyl group and a benzoylsulfamoyl group.

Particularly preferred combinations as the phthalocyanine compound represented by the general formula (I) are as follows.

(A) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
₇ and R ₈ are each independently a hydrogen atom or a halogen atom or a cyano group, particularly a hydrogen atom or a halogen atom, and among them, a hydrogen atom is most preferred.

(B) W₁, W_Two, W_Three, W_FourAt least one of
One is that the Hammett's substituent constant σp value is 0.20 or more.
Sulfamoyl group, sulfonyl group
Group, sulfinyl group, sulfonylsulfamoyl group,
Silsulfamoyl group, among which sulfamoi
And a sulfonyl group. Furthermore, W
₁, W_Two, W_Three, W_FourAt least one of the ionic hydrophilic
Group as a substituent. Among them, W₁, W_Two,
W_Three, W_FourEach independently with an ionic hydrophilic group as a substituent
Are most preferred. Ionicity as a substituent
Hydrophilic groups include sulfo groups, carboxyl groups, and quaternary
Ammonium, sulfonylsulfamoyl and acyl
Rusulfamoyl group, among which sulfo group, sulfo group
Honylsulfamoyl group and acylsulfamoyl group
Are preferable, and a sulfo group is particularly preferable.

(C) l, m, n, and p are each independently an integer of 1 or 2, and particularly preferably 1.

(D) M is a hydrogen atom, a metal element or a metal oxide, a metal hydroxide or a metal halide, particularly preferably Cu, Ni, Zn or Al, and particularly preferably Cu.

The phthalocyanine compound represented by the general formula (I) has at least one or more ionic hydrophilic groups in the molecule, and thus has good solubility or dispersibility in an aqueous medium.

From such a viewpoint, it is preferable that one molecule of the phthalocyanine compound represented by the general formula (I) has at least four or more ionic hydrophilic groups. One is preferably a sulfo group, and among them, those having at least four sulfo groups in one molecule of the phthalocyanine compound are most preferable.

Among the phthalocyanine compounds represented by the general formula (I), a phthalocyanine compound having a structure represented by the general formula (II) is more preferable. Hereinafter, the phthalocyanine compound represented by the general formula (II) of the present invention will be described in detail.

[0118]

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In the general formula (II), W ₁ , W ₂ , W ₃ ,
W ₄ is independently an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, particularly a sulfamoyl group, a sulfonyl group, a sulfinyl group, a sulfonylsulfamoyl group, and an acylsulfamoyl group; Among them, a sulfamoyl group and a sulfonyl group are most preferable. Further, at least one of W ₁ , W ₂ , W ₃ and W ₄ has an ionic hydrophilic group as a substituent. Among them, those having an ionic hydrophilic group as a substituent in each of W ₁ , W ₂ , W ₃ and W ₄ are most preferred. The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, and a quaternary ammonium group, a sulfonylsulfamoyl group, and an acylsulfamoyl group, and among them, a sulfo group, a sulfonylsulfamoyl group, and an acylsulfamoyl group. Famoyl groups are preferred, and sulfo groups are particularly preferred.

L, m, n, p and M have the same meanings as l, m, n, p and M in the formula (I), and preferred examples are also the same.

Among the phthalocyanine compounds represented by formula (II), particularly preferred combinations of substituents are the same as the particularly preferred combinations of substituents in formula (I).

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

Among the phthalocyanine compounds represented by the general formula (II), a phthalocyanine compound having a structure represented by the general formula (III) is more preferable. Hereinafter, the phthalocyanine compound represented by the general formula (III) of the present invention will be described in detail.

[0124]

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In the general formula (III), W₁, W_Two, W_Three,
W_FourAre each independently -SO-Z and / or -S
O_Two-Z and / or -SO_TwoNY₁Y_TwoAnd / or -S
O _TwoNY_ThreeSO_TwoY_TwoAnd / or -SO2NY_ThreeCOY_TwoTo
Represent.

Z is each independently 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.

Y ₁ is each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group; Represents a substituted or unsubstituted heterocyclic group.

Y ₂ is each independently 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.

Y ₃ is each independently hydrogen atom, lithium, sodium, potassium, 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, or a substituted or unsubstituted heterocyclic group.

The alkyl groups represented by Z, Y ₁ , Y ₂ and Y ₃ include an alkyl group having a substituent and an unsubstituted alkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms excluding a substituent is preferable. 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,
n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, t-butyl, hydroxyethyl,
Methoxyethyl, cyanoethyl, trifluoromethyl,
Each group such as 3-sulfopropyl and 4-sulfobutyl is included.

The cycloalkyl groups represented by Z, Y ₁ , Y ₂ and Y ₃ include a substituted cycloalkyl group and an unsubstituted cycloalkyl group. As the cycloalkyl group, a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl groups represented by Z, Y ₁ , Y ₂ and Y ₃ include alkenyl groups having a substituent and unsubstituted alkenyl groups. As the alkenyl group, an alkenyl group having 2 to 12 carbon atoms when a substituent is removed is preferable. 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 Z, Y ₁ , Y ₂ and Y ₃ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of aralkyl groups include benzyl, and 2-
Phenethyl groups are included.

The aryl group represented by Z, Y ₁ , Y ₂ and Y ₃ includes a substituted aryl group and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of aryl groups include phenyl, p-tolyl, p-
Methoxyphenyl, o-chlorophenyl and m- (3
-Sulfopropylamino) phenyl and the like.

The heterocyclic group represented by Z, Y ₁ , Y ₂ and Y ₃ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group, and the heterocyclic group is further condensed with another ring. May be formed.

Preferred examples of the hetero ring and its condensed ring include, without limitation, the substitution position of the hetero ring, and each independently represents imidazole, benzimidazole, pyrazole, benzopyrazole, triazole, thiazole, benzothiazole, isothiazole, Benzoisothiazole, oxazole, benzoxazole, thiadiazole, pyrrole, benzopyrrole, indole, isoxazole, benzisoxazole, thiophene, benzothiophene, furan, benzofuran, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, cinnoline, phthalazine, Quinazoline, quinoxaline and the like.

Preferred examples of the hetero ring and its condensed ring are a 5- to 6-membered nitrogen-containing hetero ring (furthermore, a condensed ring can be formed with another ring). However, when Z forms a 6-membered nitrogen-containing heterocycle (which can form a condensed ring with another ring), the number of nitrogen atoms constituting the 6-membered nitrogen-containing heterocycle is 1 or 2 (6 members). A nitrogen-containing heterocyclic ring having three or more nitrogen atoms, for example, excluding a triazine ring).

More preferable examples of the 5- to 6-membered nitrogen-containing heterocyclic ring and the condensed ring thereof are given below without limiting the substitution position of the heterocyclic ring. Each of them is independently imidazole, benzimidazole, pyrazole, benzopyrazole, triazole, thiazole. , Benzothiazole, isothiazole,
Benzoisothiazole, oxazole, benzoxazole, thiadiazole, pyrrole, benzopyrrole, indole, isoxazole, benzisoxazole, pyridine, quinoline, isoquinoline, pyridazine,
Pyrimidine, pyrazine, cinnoline, phthalazine, quinazoline, etc., each ring group, more preferably imidazole, benzimidazole, pyrazole, benzopyrazole, triazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, oxazole,
It is each ring group such as benzoxazole, thiadiazole, pyrrole, benzopyrrole, indole, isoxazole, and benzoisoxazole, and among them, each ring group such as pyrazole, triazole, benzothiazole, and benzoisothiazole is most preferable.

Examples of the substituent of the 5- or 6-membered nitrogen-containing heterocycle and the condensed ring thereof include an ionic hydrophilic group.

In the general formula (III), l, m, n, p
And M are l, m, and m in the general formula (II), respectively.
It has the same meaning as n, p and M, and preferred examples are also the same.
A particularly preferred water-soluble phthalocyanine compound has a maximum absorbance b in an absorption band from 660 nm to 680 nm in a spectral absorption curve of an aqueous solution, and a maximum absorbance b from 600 nm to 640 nm.
Is a water-soluble phthalocyanine compound having an absorbance ratio b / a to the maximum absorbance a in the absorption band of less than 0.8 and represented by the general formula (III). The general formula (II
In the phthalocyanine compound represented by I), the oxidation potential of the phthalocyanine compound is 1.1 eV (vsSC
More preferably, the phthalocyanine compound is nobler than E).

However, the phthalocyanine compound represented by the general formula (III) has at least four or more ionic hydrophilic groups in one molecule.

Particularly preferred combinations as the phthalocyanine compound represented by the general formula (III) are as follows. (A) W ₁ , W ₂ , W ₃ , and W ₄ are each independently -S
O-Z and / or -SO ₂ -Z and / or -SO ₂ N
Y ₁ is Y ₂ and / or -SO ₂ NY ₃ SO ₂ Y _2, and / or -SO2NY ₃ COY _2, -SO ₂ -Z Among them
And / or -SO ₂ NY ₁ Y ₂ and / or -SO ₂ NY
₃ SO ₂ Y ₂ is preferred, and —SO ₂ —Z and / or —SO
₂ NY ₁ Y ₂ is most preferred. Further, W ₁ , W ₂ , W ₃ , W ₄
Has an ionic hydrophilic group as a substituent. Among them, those having an ionic hydrophilic group as a substituent independently of each of W ₁ , W ₂ , W ₃ and W ₄ are most preferred. The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, and a quaternary ammonium group, a sulfonylsulfamoyl group, and an acylsulfamoyl group, and among them, a sulfo group, a sulfonylsulfamoyl group, and an acylsulfamoyl group. Famoyl groups are preferred, and sulfo groups are particularly preferred.

(B) l, m, n, and p are each independently an integer of 1 or 2, and particularly preferably 1.

(C) M is a hydrogen atom, a metal element or a metal oxide, a metal hydroxide or a metal halide, particularly preferably Cu, Ni, Zn or Al, and particularly preferably Cu.

Since the phthalocyanine compound represented by the general formula (III) has at least one ionic hydrophilic group in the molecule, the solubility or dispersibility in an aqueous medium is improved.

Particularly preferred phthalocyanine compounds are phthalocyanine compounds represented by the general formula (III) wherein the ionic hydrophilic group is a carboxyl group, a sulfo group,
It is a phthalocyanine compound which is a group selected from a quaternary ammonium group, a sulfonylsulfamoyl group and an acylsulfamoyl group. From such a viewpoint, it is preferable that one molecule of the phthalocyanine compound represented by the above general formula (III) has at least four or more ionic hydrophilic groups.
Preferably, the phthalocyanine compound has at least four sulfo groups in one molecule of the phthalocyanine compound.

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

In general, it is known to use various phthalocyanine derivatives as an ink composition for ink jet. The phthalocyanine derivative represented by the following general formula (IV) is inevitably substituted at the time of its synthesis.
_n (n = 1 to 16, R is simply a substituent and does not mean that all of R _n are the same type of substituent) (R ₁ : 1 to R ₁₆ : 16 And defined here)
Although it may contain isomers, these substituted positional isomers are often regarded as the same derivative without distinction from each other. Further, when isomers are included in the substituent of R, these are often regarded as the same phthalocyanine derivative without distinction.

[0149]

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In the present specification, the case where the structure of the phthalocyanine compound is different means that, as described in the above general formula (IV), when the constituent atoms of the substituent Rn (n = 1 to 16) are different, the number of substituents is different. Either they are different or the substitution positions are different.

In the present invention, the above-mentioned general formulas (I) to (II)
Derivatives having different structures (particularly, substitution positions) of the phthalocyanine compound represented by I) are defined by classifying them into the following three types.

(1) β-substituted type: (2 and / or 3
Phthalocyanine compounds having specific substituents at positions 6, 6 and / or 7, 10 and / or 11, 14 and / or 15)

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

(3) α, β-position mixed substitution type: (phthalocyanine compound having a specific substituent in the 1 to 16 positions without regularity)

In the present specification, when describing a derivative of a phthalocyanine compound having a different structure (particularly, a substitution position), 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 include, for example, "Phthalocyanine-Chemistry and Function-" (P.1-62) published by Shirai-Kobayashi Co., Ltd.
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 described in World Patents 00/17275 and 00/17275.
08103, 00/08101, 98/4185
3. As described in JP-A-10-36471, for example, when the unsubstituted phthalocyanine compound is synthesized through sulfonation, sulfonyl chloride, or amidation, sulfonation is performed at any substitution position of the phthalocyanine nucleus. The number that can occur and is sulfonated is also difficult to control (especially a mixture of one to four).

Therefore, when a sulfo group is introduced under such reaction conditions, the substitution position and the number of substitution of the sulfo group introduced into the product cannot be specified, and the mixture having different numbers of substitution groups or substitution positions is inevitable. give.

Therefore, when the compound of the present invention is synthesized and used as a starting material, W ₁ , W ₂ , W ₃ ,
Since selective introduction of W ₄ is difficult (for example, the number and substitution position of substituted sulfamoyl groups cannot be specified), to isolate the compound of the present invention, several compounds having different numbers of substitution groups and substitution positions are required. It is necessary to completely separate the contained mixture (α, β-position mixed substitution type). If separation is not possible, it can be defined as a phthalocyanine compound completely different from the compound of the present invention. (Specific substituents: W ₁ , W ₂ , W ₃ , and W ₄ are replaced with a specific number (1 and / or 2)
It is obvious within the common sense of organic synthesis that the compound is not an introduced phthalocyanine compound. )

The absorption characteristics (absorbance ratio b / a value) of the spectral absorption curve of the aqueous solution of the phthalocyanine compound of the present invention.
It has been found that the reason for showing the preferred value is due to the structural feature of being a β-type phthalocyanine compound as a result of a detailed study, and that this structure is also very important especially for improving the robustness of the formed image. It could be confirmed.

Further, as described above, when a large number of electron-withdrawing groups such as a sulfonyl group and a sulfamoyl group are introduced into the phthalocyanine nucleus, the oxidation potential becomes more noble.
It was also found that the ozone gas resistance of the formed image was increased.

However, when trying to synthesize the phthalocyanine compound of the present invention according to the above synthesis method, the number of introduced electron-withdrawing groups per phthalocyanine compound molecule is small. Along with that, it is inevitable that a phthalocyanine compound whose oxidation potential is more base is mixed in,
This results in a decrease in ozone gas resistance of the formed image.

Therefore, in order to synthesize the phthalocyanine compound of the present invention (having a specific spectral absorption characteristic and a specific oxidation potential), it is more preferable to use the following synthesis method. Can be introduced at a specific substitution position (β-position) by a specific number.
However, the starting material, phthalocyanine compound intermediate and synthetic route are not limited to these.

In particular, as in the present invention, when it is desired to introduce an electron withdrawing group at a specific number and a specific position in order to have a specific spectral absorption characteristic and a specific oxidation potential, the following synthesis method is used. It is extremely superior to the method.

For example, the phthalocyanine compound represented by the general formula (V) of the present invention is, for example, a phthalonitrile compound represented by the general formula (VI) and / or a diiminoisoindoline derivative represented by the general formula (VII) And general formula (VIII)
Or a 4-sulfophthalonitrile derivative (compound R) represented by the following formula:
And a metal derivative represented by the general formula (VIII) to obtain a tetrasulfophthalocyanine compound.

[0166]

Embedded image

(In the formulas (VI) and / or (VII), R represents a substituted sulfamoyl group, a substituted sulfonyl group, a substituted sulfonylsulfamoyl group, etc.)

Formula (VIII): M- (Y) d (in Formula (VIII), M is the same as M in Formulas (I) to (III), Y is a halogen atom, an acetate anion, Represents a monovalent or divalent ligand such as acetylacetonate or oxygen, and d is an integer of 1 to 4.) As the metal derivative represented by the formula (VIII), Al, S
i, Ti, V, Mn, Fe, Co, Ni, Cu, Zn,
Examples include halides of Ge, Ru, Rh, Pd, In, Sn, Pt, and Pb, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, and complexes. 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, zinc acetate, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, manganese chloride, chloride Examples include lead, lead acetate, indium chloride, titanium chloride, tin chloride and the like.

The amounts of the above metal derivative and the phthalonitrile compound represented by the general formula (VI) are from 1: 3 to
1: 6 is preferred. In addition, the above metal derivative and the general formula (VI
The amount of the diiminoisoindoline derivative represented by I) to be used is preferably from 1: 3 to 1: 6 in molar ratio.

The reaction is usually performed in the presence of a solvent. As the solvent, an organic solvent having a boiling point of 80 ° C. or higher, preferably 130 ° C. or higher is used. For example, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol,
Benzyl alcohol, ethylene glycol, propylene glycol, 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 of the phthalonitrile compound or diiminoisoindoline derivative is 0.1 to 10 moles, preferably 0.5 to 2 moles, per 1 mole.

The reaction temperature is usually in the range of 80 to 300 ° C., preferably 100 to 250 ° C., particularly preferably 130 to 230 ° C. If the temperature is lower than 80 ° C., the reaction rate is extremely slow. If the temperature exceeds 300 ° C., the phthalocyanine compound may be decomposed.

The reaction time is usually in the range of 2 to 20 hours, preferably in the range of 5 to 15 hours, particularly preferably in the range of 5 to 10 hours. If the time is less than 2 hours, a lot of unreacted raw materials are present,
If the time exceeds 0 hours, the phthalocyanine compound may be decomposed.

The products obtained by these reactions are used according to a usual post-treatment method of an organic synthesis reaction and then purified or used without purification. That is, for example, without purifying what is released from the reaction system,
Alternatively, recrystallization, column chromatography (for example,
Gel permeation chromatography (SEPHADE
^XTM LH-20 (manufactured by Pharmacia) or the like can be used alone or in combination to provide a product.

After the completion of the reaction, the reaction solvent is distilled off, or the residue is poured into water or ice without distillation, neutralized or liberated without neutralization. The product can be provided as a product 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 extracted with an organic solvent / aqueous solution is neutralized by adding it to water or ice without being distilled off, or is not neutralized, or is purified by crystallization or column chromatography. After performing these operations alone or in combination, the product can be provided as a product.

The thus obtained phthalocyanine compound represented by the general formula (V) is usually represented by the following general formula (a)-
1 to (a) -4. These four compounds are isomers in which the substitution positions of R _{1 to} R ₄ are different.

[0178]

Embedded image

[0179]

Embedded image

[0180]

[Formula 14]

[0181]

[Formula 15]

The compounds represented by the general formulas (a) -1 to (a) -4 may be substituted at β-position (positions 2 and / or 3, 6 and / or 7, 10 and / or 11, 14 and Or a phthalocyanine compound having a specific substituent at the 15-position)
Is a compound having a completely different structure (substitution position) from the α-substituted type and the α, β-position mixed substituted type, and is a structural feature which is extremely important as a means for achieving the object of the present invention.

That is, in the present invention, in any of the substituted types, specific substituents represented by, for example, W ₁ , W ₂ , W ₃ and W ₄ in the general formula (I) are very effective in improving the robustness. Very important to.

Further, specific substituents (W ₁ , W ₂ , W ₃ ,
W ₄ ) is a specific number (β-substituted type) at a specific number {for example, in the case of a phthalocyanine nucleus represented by the general formula (IV), (2 and / or 3), (6 and Or 7
Position), (positions 10 and / or 11) and (positions 14 and / or 15) each include at least one of the above specific substituents.
The compound introduced into the phthalocyanine nucleus is a very important structural feature as a means for achieving the object of the present invention.

In the present invention, a water-soluble phthalocyanine compound (β-type phthalocyanine compound) having a specific spectral absorption characteristic (absorbance ratio b / a value is less than 1) is very important for improving the robustness of a formed image. Was found.

That is, the spectral absorption curve obtained by measuring the aqueous solution of the water-soluble phthalocyanine compound of the present invention with a spectrophotometer in accordance with JIS Z8120-86 is from 660 nm to 68.
The maximum absorbance b in the absorption band reaching 0 nm is attributed to the monomer absorption, and the maximum absorbance a in the absorption band from 600 nm to 640 nm is attributed to the association absorption. (Degree of state) greatly affects the fastness of the formed image.

The aggregate of the water-soluble phthalocyanine compound in the present invention refers to an aggregate of two or more phthalocyanine molecules. When the aggregate of the phthalocyanine compound is used, the stability to light, heat, and an oxidizing gas (particularly, ozone gas) is remarkably improved as compared with a single molecular dispersed state. In addition, the formation of the aggregate significantly improves the cyan hue of the absorption spectrum (excellent absorption characteristics as a cyan dye for an image forming material).

Whether or not the dye is associated is determined, for example, by
As explained in Wright, JD (Translated by Eguchi Taro), “Molecular Crystals” (Chemical Doujin), it can be easily determined from the shift of the absorption maximum (λmax) in the absorption spectrum. J-aggregates that shift to the shorter side, and H-aggregates that shift to the shorter wave side. In the present invention, the water-soluble phthalocyanine aggregate forms an aggregate by shifting the absorption maximum to the shorter wavelength side, and utilizes this aggregate.

Therefore, the specific spectral absorption characteristics (absorbance ratio b /
The structural feature of the water-soluble phthalocyanine compound having the value of a value <1: promotion of the association state) is based on the specific substituents (W ₁ , W ₂ , W ₃ , W _{4 described above} , especially A compound in which a specific number of groups (especially, a sulfamoyl group or a sulfonyl group) are introduced at a specific position (β-substituted type) in a specific number (β-position substitution type) into a phthalocyanine mother nucleus promotes an association state and is the most preferable structure in terms of image fastness and hue I came to find that.

Furthermore, it has been found that the fact that the oxidation potential of the water-soluble phthalocyanine compound is more noble than 1.0 V (vs SCE) is very important for improving the fastness of the formed image.

That is, specific substituents (W ₁ , W ₂ ,
The water-soluble phthalocyanine compound of the present invention in which a specific number of W ₃ and W ₄ ) were selectively introduced at a specific substitution position (β-position) was excellent in hue, light fastness, ozone gas resistance and the like.

The causes of these are not known in detail, but are estimated as follows: specific spectral absorption characteristics (promotion of association state of phthalocyanine compound); specific oxidation potential (for example, phthalocyanine compound and electrophile It is considered that the phthalocyanine compound of the present invention having (reducing discoloration due to oxidation reaction with ozone gas as a reagent) is based on a specific substituent (by β-position substitution type).

[0193] In this specification, the term "ozone gas resistance" refers to the resistance to ozone gas as a representative, and includes the resistance to oxidizing atmospheres other than ozone gas. That is, the phthalocyanine compound represented by the general formula (I) according to the present invention is a nitrogen oxide that is often present in exhaust gas from automobiles, and a sulfur oxide that is often present in exhaust gas from thermal power plants and factories. Oxidation present in the general environment, such as ozone gas generated by a radical chain reaction, photochemical smog rich in oxygen-nitrogen or oxygen-hydrogen radicals, and hydrogen peroxide radicals generated from places using special chemicals such as beauty salons It is characterized by strong resistance to reactive gases. Therefore, when the oxidative deterioration of an image such as an outdoor advertisement or guidance in a railway facility limits the life of the image, by using the phthalocyanine compound according to the present invention as an image forming material, resistance to an oxidizing atmosphere, that is, So-called ozone gas resistance can be improved.

Specific examples of the phthalocyanine compound of the present invention are shown in Tables 1 to 10 below (exemplified compounds 101 to 175).
It is not limited to the following example.

[0195]

[Table 1]

[0196]

[Table 2]

[0197]

[Table 3]

[0198]

[Table 4]

[0199]

[Table 5]

[0200]

[Table 6]

[0201]

[Table 7]

[0202]

[Table 8]

[0203]

[Table 9]

[0204]

[Table 10]

Examples of uses of the phthalocyanine compound according to the present invention include a material for forming an image, particularly a color image. Specifically, the phthalocyanine compound includes an ink-jet recording material described in detail below, and a heat-sensitive transfer type image. Recording materials, pressure-sensitive recording materials, recording materials using an electrophotographic method, transfer-type silver halide photosensitive materials, printing inks, recording pens, and the like, preferably ink jet recording materials, thermal transfer image recording materials, and electrophotographic methods , And more preferably an ink jet recording material. Also,
The present invention can also be applied to a color filter used in solid-state imaging devices such as LCDs and CCDs described in U.S. Pat. No. 4,808,501 and JP-A-6-35182, and a dyeing solution for dyeing various fibers.

The compound of the present invention can be used after adjusting physical properties such as solubility and heat transfer property suitable for the use thereof by a substituent. Further, the compound 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 Jet Ink] Next, the ink jet ink of the present invention will be described. The inkjet ink can be produced by dissolving and / or dispersing the phthalocyanine compound 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 anti-drying agent is preferably 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,
Polyhydric alcohols represented by dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-
Heterocycles such as 2-imidazolidinone and N-ethylmorpholine; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 3-sulfolene; polyfunctional compounds such as diacetone alcohol and 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 anti-drying agents are preferably contained in the ink in an amount of 10 to 50% by weight.

The penetration enhancer is suitably used for the purpose of better penetrating the ink for ink jet into paper. As the penetration enhancer, 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 can be used. . These are usually effective enough if contained in the ink in an amount of 5 to 30% by weight.
It is preferable to use it in the range of the amount of addition which does not cause bleeding of printing and paper missing (print-through).

[0211] The ultraviolet absorber is used for the purpose of improving the storability of an image. JP-A-5858 as an ultraviolet absorber
No. 185677, No. 61-90537,
JP-A-2-782, JP-A-5-1970075,
Benzotriazole compounds described in JP-A-9-34057 and the like; JP-A-46-2784;
No. 194483, U.S. Pat. No. 3,214,463, and the like.
Nos. 0492 and 56-21141,
0-88106, cinnamic acid-based compounds, and the like;
JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, and JP-A-10-182621
Compounds disclosed in Japanese Unexamined Patent Application Publication No. Hei 8-501291, Research Disclosure N
o. No. 24239, stilbene compounds,
A compound that absorbs ultraviolet light and emits fluorescence, typically a benzoxazole-based compound, that is, a so-called fluorescent whitening agent, can also be used.

The anti-fading agent is used for the purpose of improving the storability of an image. As an anti-fading agent, various organic and metal complex-based anti-fading agents can be used.
Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like. Complexes and zinc complexes. More specifically, Research Disclosure No. 176
No. 43, Nos. VII, I through J; 15162; No. 18716, left column, page 650; 36544
No. 527, ibid. Page 872 of 307105, N
o. Compounds described in the patent cited in US Pat. No. 15,162, and the compounds represented by the general formulas and compound examples of typical compounds described on pages 127 to 137 of JP-A-62-215272 can be used.

Sodium dehydroacetate as a fungicide,
Sodium benzoate, sodium pyridinethione-1-
Oxides, p-hydroxybenzoic acid ethyl ester,
Examples thereof include 1,2-benzisothiazolin-3-one and salts thereof. These are contained in the ink in an amount of 0.02 to 1.0.
It is preferred to use 0% by weight.

As the pH adjusting agent, the above neutralizing agents (organic bases, inorganic alkalis) can be used. For the purpose of improving the storage stability of the inkjet ink, the pH adjuster is preferably added to the inkjet ink at a pH of 6 to 10 for summer use, and more preferably added to a pH of 7 to 10 for the summer.

Examples of the surface tension modifier include nonionic, cationic and anionic surfactants. The surface tension of the inkjet ink of the present invention is 25 to 70 m.
Pa · s is preferred. Further, it is preferably 25 to 60 mN / m. In addition, the viscosity of the inkjet ink of the present invention is 3
It is preferably 0 mPa · s or less. It is more preferable to adjust the pressure to 20 mPa · s or less. Examples of surfactants include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates,
Anionic surfactants such as dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, and polyoxyethylene Nonionic surfactants such as fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and oxyethylene oxypropylene block copolymers are preferred. Also, acetylene-based polyoxyethylene oxide surfactant S
URFYNOLS (Air Products & Chem
icals) is also preferably used. Also, N, N-
Also preferred are amine oxide amphoteric surfactants such as dimethyl-N-alkylamine oxide. Further, Japanese Patent Application Laid-Open No. 59-157,636, pages (37) to (38), Research Disclosure No. 308119 (1989)
Those mentioned as the surfactants described 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 as required.

In the case where the phthalocyanine compound of the present invention is dispersed in an aqueous medium, JP-A-11-286637, Japanese Patent Application No.
No. 78491, No. 2000-80259, or disperse colored fine particles containing a dye and an oil-soluble polymer in an aqueous medium as in No. 2000-62370, and Japanese Patent Application Nos. 2000-78454 and 2000-78491.
It is preferable to disperse the phthalocyanine compound of the present invention dissolved in a high-boiling organic solvent as described in JP-A Nos. 2000-203856 and 2000-203857 in an aqueous medium. Specific method for dispersing the phthalocyanine compound of the present invention in an aqueous medium,
As the oil-soluble polymer, high-boiling organic solvent, additive and the amount thereof to be used, those described in the above patent can be preferably used. Alternatively, the azo compound may be dispersed as fine particles in a solid state. When dispersing,
Dispersants and surfactants can be used. As a dispersing device, a simple stirrer or impeller stirring method, in-line stirring method, mill method (for example, a colloid mill,
Ball mill, sand mill, attritor, roll mill,
Agitator mill, etc.), ultrasonic method, high-pressure emulsification dispersion method (high-pressure homogenizer; specific commercially available devices include Gaulin homogenizer, microfluidizer, DeB
EE2000) can be used. Regarding the method for preparing the above-mentioned ink-jet ink, besides the above-mentioned patents, JP-A-5-148436 and 5-29531
No. 2, 7-97541, 7-82515, 7
The details are described in JP-A-118584, JP-A-11-286637, and Japanese Patent Application No. 2000-87539, and can also be used for preparing the inkjet ink 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.

In 100 parts by weight of the ink-jet ink of the present invention, the phthalocyanine compound is contained in an amount of from 0.2 part by weight to 1 part by weight.
It is preferred that the content be 0 parts by weight or less. Further, other colorants may be used together with the phthalocyanine compound in the inkjet ink of the present invention. When two or more colorants are used in combination, the total content of the colorants is preferably in the above range.

The ink-jet ink of the present invention can be used not only for forming a single-color image but also for forming a full-color image. In order to form a full-color image, magenta color ink, cyan color ink, and yellow color ink can be used, and in order to adjust color, black color ink may be further used. In these inks, other color materials (dyes and pigments) can be used in addition to the phthalocyanine compound according to the present invention to improve the image reproduction performance.

Along with the phthalocyanine compound of the present invention,
Any applicable yellow dye can be used. For example, phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone as coupling components (hereinafter referred to as coupler components),
Aryl or hetenylazo dyes having open-chain active methylene compounds, etc .; azomethine dyes having open-chain active methylene compounds, etc. as coupler components; methine dyes such as benzylidene dyes and monomethine oxonol dyes; naphthoquinone dyes, for example ,
There are quinone dyes such as anthraquinone dyes and the like, and other dyes 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.

Any applicable cyan dye can be used. For example, aryl or hetenylazo 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-mentioned dyes may exhibit each color of yellow, magenta and cyan only after a part of the chromophore is dissociated. In this case, the counter cation is 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.

[Inkjet recording method] In the inkjet recording method of the present invention, a known image receiving material, that is, plain paper,
Resin-coated paper, for example, JP-A-8-169172,
JP-A-8-27693, JP-A-2-276670,
JP-A-7-276789, JP-A-9-323475, JP-A-62-238873, JP-A-10-1
Nos. 53988, 10-217473, 1
Nos. 0-235999, 10-337947, 10-217597, and 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 or water resistance or 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, 2000-299465
And JP-A-2000-297365 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.
/ M2 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 derivative. 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 lightfastness 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 these waterproofing agents, cationic resins are particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably from 1 to 15% by weight, more preferably from 3 to 15% by weight, based on the total solid content of the ink receiving layer.
Preferably it is 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.

Surfactants include coating aids, release improvers,
It functions as a slipperiness improver or an antistatic agent.
Regarding the surfactant, JP-A-62-173463,
It is described in each publication of JP-A-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). For organic fluoro compounds, see
No. 9053 (columns 8 to 17), JP-A-61-20994
And JP-A-62-135826. Other additives added to the ink receiving layer include a pigment dispersant, a thickener, a defoamer, a dye, a fluorescent whitening agent, a preservative,
pH adjusters, matting agents, hardeners 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.

As the aqueous binder contained in the back coat layer, 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 the respective publications 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 in which ink is ejected by using electrostatic attraction, a drop-on-demand method in which vibration pressure of a piezo element is used. (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.

[0238]

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

[Example 1] Deionized water was added to the following components to make 1 liter, and the mixture was heated at 30 to 40 ° C to obtain 1 liter.
Stirred for hours. Then, pH is adjusted to 10 mol / L with KOH.
= 9, and filtered under reduced pressure through a microfilter having an average pore size of 0.25 μm to prepare a cyan ink liquid A.

Composition of ink liquid A: phthalocyanine compound (101) of the present invention 20.0 g diethylene glycol 20 g glycerin 120 g diethylene glycol monobutyl ether 230 g 2-hydroxylithone 80 g triethanolamine 17.9 g benzotriazole 0.06 g Surfynol TG 8.5 g PROXEL XL2 1.8 g

Ink liquids B to G were prepared in the same manner as in preparation of ink liquid A, except that the phthalocyanine compound was changed as shown in Table 11 below. At this time, as a comparative ink liquid, an ink liquid 10 was prepared using the following compounds.
1,102,103,104 were created.

[0242]

Embedded image

[0243]

Embedded image

In the case of changing the dye, the dye was used such that the addition amount 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 G) and comparative examples (ink liquids 101 to 104)
The following evaluation was performed about the ink-jet ink. The results are shown in Table-11. In Table 11, "color tone", "paper dependence", "water resistance" and "light fastness" indicate that each inkjet ink is an inkjet printer (manufactured by EPSON Corporation; PM-700C).
Photo glossy paper (EPSON PM photo paper <glossy> (K
(A420PSK, EPSON).

<Color Tone> The reflection spectrum of the image formed on the photo glossy paper at intervals of 10 nm in the 390-730 nm region was measured, and this was measured based on the CIE (International Commission on Illumination) L * a * b * color space system. , A *, b *
Was calculated. A preferable color tone for cyan was defined as follows as compared with a standard cyan color sample of JAPAN Color of JNC (Japan Printing Machinery Association).

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

<Paper Dependency> The color tone of the image formed on the photo glossy paper and the image separately formed on the plain paper for PPC were 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> A weather meter (Atlas Weather-O.
Meter C. I65, Atlas, Illinois, USA
Xenon light (85000 lx) for 7 days using a densitometer (X).
-Rite310TR) and evaluated as a dye residual ratio. The reflection densities were 1, 1.5 and 2.
It was measured at three points of 0. The dye remaining rate is 70 at any concentration.
% Or less, B was evaluated when less than 70% at one or two points, and C was evaluated when less than 70% at all concentrations.

<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 Gas Resistance> While passing dry air through the double glass tube of the Siemens type ozonizer, 5 kV
An AC voltage is applied and the ozone gas concentration is adjusted to 0.
In a box set at 5 ± 0.1 ppm, room temperature, and dark place, place the photo glossy paper on which the image is formed in a box set at an ozone gas concentration of 0.5 ± 0.1 ppm, room temperature, and dark place. After standing for 7 days, the image density before and after standing under ozone gas was measured using a reflection densitometer (X-Rite310TR), and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. A: When the residual ratio of the dye was 70% or more at any concentration, A: 1 or 2 points: less than 70%; B: 70% at all concentrations
The case of less than C was evaluated in three steps.

<Spectral Absorption> A phthalocyanine compound of the present invention is weighed in a fixed amount (in terms of molecular weight), diluted with distilled water, and diluted with distilled water (with the larger one of absorbance a and absorbance b being 0.85 to 0.85). After diluting so as to fall within the range of 1.00), analysis was performed with a spectrophotometer under the following measurement conditions. Table 11 shows the measurement results of the phthalocyanine compound used in the examples. (Measurement conditions) Apparatus used: Shimadzu self-recording spectrophotometer UV-260 Cell: Quartz cell, optical path length 10 mm; Measurement temperature: 20 ° C; Diluent: distilled water (pH = 7.0)

Exemplary compounds 101 and 10 of the phthalocyanine compound of the present invention used in inks A to G shown in Table 1.
FIGS. 2 to 5 show the spectral absorption curves of the aqueous solutions of 5, 108, 112, 131, 132, 133 and Comparative Compounds 1 to 4 determined by a spectrophotometer. The measurement was performed by diluting with distilled water such that the maximum absorbance b of the aqueous solution was 1.0.

FIG. 2 shows exemplified compounds 101 and 1 of the present invention.
FIG. 3 of Examples 05 and 108 shows exemplary compounds 112 and 13
1 and 132, FIG. 4 shows Exemplary Compound 133 and Comparative Compounds 1 and 2, and FIG. 5 shows Comparative Compounds 3 and 4.
, Respectively, show spectral absorption curves at 350 to 700 nm, and the vertical axis indicates absorbance (ABS). The wavelengths shown in the upper right margin of each figure indicate the respective maximum absorption wavelengths. Absorbance ratio b / a determined from these spectral absorption curves
Is shown in Table 11.

<Oxidation potential> The value of the oxidation potential was determined according to the present invention.
Weigh a certain amount (converted to molecular weight) of a tarocyanine compound
0.1moldm^-3Of tetrapropylammonium perchlorate
N, N-dimethylform containing nitrogen as supporting electrolyte
In amide (dye concentration is 0.001 moldm ^-3) At DC
It was measured by polarography. Polarography
The device has a carbon (GC) electrode as the working electrode and a counter electrode
Using a rotating platinum electrode to sweep to the oxidation side (noble side).
Of the oxidized wave by linear approximation and its intersection with the peak value and residual charge
The midpoint of the intersection with the flow value is the oxidation potential value (vs SCE)
Was. Phthalocyanine compounds used in Examples and comparative compounds
Table 11 shows the measurement results of the products.

[0257]

[Table 11]

As is clear from Table 11, 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 of Example 1, and the same evaluation as in Example 1 was performed. Example 1
The same result as was obtained.

Example 3 The same ink prepared in Example 1 was used in an ink jet printer BJ-F850 (CA
Example 1) An image was printed on the photo glossy paper GP-301 of the company using the same machine.
The same evaluation as in Example 1 was performed, and the same result as in Example 1 was obtained.

Example 4 A test was performed using the same procedure as in Example 1 except that the test method of Example 1 was changed to the following environmental test method. In other words, as an oxidizing gas resistance test method that simulates an oxidizing gas such as automobile exhaust gas and an outdoor environment exposed to sunlight, H.Iw
ano, et al; Journal of Imaging Science and Technol
ogy, Vol. 38, 140-142 (1944), using an oxidation resistance test method with a relative humidity of 80%, a hydrogen peroxide concentration of 120 ppm, and a fluorescent lamp irradiation chamber. The results of the test were the same as those in Example 1.

[0262]

According to the present invention, 1) it contains a phthalocyanine compound having absorption characteristics excellent in color reproducibility and having sufficient fastness to light, heat, humidity and an active gas in the environment. 2) An ink composition for printing such as inkjet (particularly inkjet ink) to which the coloring composition is applied, an ink sheet in a heat-sensitive transfer image forming material, a toner for electrophotography, LC
D 、 Provides various coloring compositions such as coloring compositions for color filters used in PDPs and CCDs, dyeing solutions for dyeing various fibers, etc. 3) Images for light and environmental active gas, especially ozone gas It is possible to provide a method for improving the robustness of a recorded matter.

[Brief description of the drawings]

FIG. 1 is a spectral absorption curve diagram for explaining an absorbance ratio b / a of a phthalocyanine compound.

FIG. 2 shows exemplary compounds 101, 105 and 10 of the present invention.
8 is a spectral absorption curve diagram of FIG.

FIG. 3 illustrates exemplary compounds 112, 131 and 13 of the present invention.
2 is a spectral absorption curve diagram of FIG.

FIG. 4 is a spectral absorption curve diagram of an exemplary compound 133 of the present invention and comparative compounds 1 and 2.

FIG. 5 is a graph showing spectral absorption curves of Comparative Compounds 3 and 4.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kaji Yabuki 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film F-term (reference) 2C056 EA13 FC02 2H025 AA10 AA11 AB13 CC12 2H086 BA56 BA60 4J039 BC60 BE06 CA03 EA16 EA34 GA24

Claims (7)

[Claims] 660 n in a spectral absorption curve of an aqueous solution
The maximum absorbance b in the absorption band from m to 680 nm and 6
Maximum absorbance a in the absorption band from 00 nm to 640 nm
Is less than 1 and the following general formula:
Containing a water-soluble phthalocyanine compound represented by (I)
A coloring composition, comprising: Embedded image(Where R₁, R_Two, R_Three, R_Four, R_Five, R₆, R₇, And R₈
Are each independently a hydrogen atom, a halogen atom, an alkyl
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
Group, arylthio group, alkoxycarbonylamino group,
Sulfonamide group, carbamoyl group, sulfamoyl
Group, sulfonyl group, alkoxycarbonyl group, heterocycle
Oxy group, azo group, acyloxy group, carbamoyloxy
A silyl group, a silyloxy group, an aryloxycarbonyl group,
Aryloxycarbonylamino group, imide group, hetero
Ring thio, sulfinyl, phosphoryl, or acyl
And each may further have a substituent.
W₁, W_Two, W_Three, W_FourIs each independently the above R₁,
R_Two, R_Three, R_Four, R_Five, R₆, R₇, And R₈Is a table
Each group or sulfonylsulfamoyl group or acyl
Represents a sulfamoyl group, each of which further has a substituent
May be. Where W₁, W_Two, W_Three, W_FourAt least one of
One is that the Hammett's substituent constant σp value is 0.20 or more.
A child attracting group, and W₁, W_Two, W _Three, W_FourLess of
One is whether it is an ionic hydrophilic group itself,
Has an ionic hydrophilic group as a substituent. l, m,
n and p represent an integer of 1 or 2. M is a hydrogen atom,
Metal element or its oxide, hydroxide or halogen
Represents a compound. ) 2. The coloring composition according to claim 1, wherein the phthalocyanine compound represented by the general formula (I) has an oxidation potential nobleer than 1.0 eV (vs SCE). 3. The coloring composition according to claim 1, wherein the phthalocyanine compound represented by the general formula (I) is a phthalocyanine compound represented by the following general formula (II). Embedded image (In Formula (II), W ₁ , W ₂ , W ₃ , and W ₄ each independently represent an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more; provided that W ₁ , W ₂ , W ₃ , W ₄
One is an ionic hydrophilic group itself or has an ionic hydrophilic group as a substituent. l, m, n, p and M are respectively l, m, and m in the general formula (I).
Synonymous with n, p and M. ) 4. The coloring composition according to claim 1, wherein the phthalocyanine compound represented by the general formula (II) is a phthalocyanine compound represented by the following general formula (III). Embedded image (In the formula (III), W ₁ , W ₂ , W ₃ , and W ₄ are each independently —SO—Z and / or —SO ₂ —Z and / or —SO ₂ NY ₁ Y ₂ and / or Represents SO ₂ NY ₃ SO ₂ Y ₂ and / or —SO ₂ NY ₃ COY ₂ , wherein Z independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group , substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, are each .Y ₁ representing a substituted or unsubstituted heterocyclic group independently, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted A cycloalkyl group, a substituted or unsubstituted alkenyl group,
Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and Y ₂ each independently represents 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, and a substituted or unsubstituted heterocyclic group. Y ₃ each independently represents a hydrogen atom, lithium, sodium, potassium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, Or an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. l, m, n, p and M have the same meanings as l, m, n, p and M in the general formula (II), respectively. However, the phthalocyanine compound represented by the general formula (III) has at least four or more ionic hydrophilic groups in one molecule. ) 5. An ink jet ink comprising the coloring composition according to claim 1. Description: 6. 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-jet ink according to claim 5. 7. A method for improving ozone gas fading resistance of an image recorded matter, wherein an image is formed using the inkjet ink according to claim 5.