JP2003321630A - Ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition for printing such as ink jet which gives a colored image and a colored material excellent in a hue and fastness and particularly ink for ink jet recording having a good hue by use of a phthalocyanine-based dye derivative and capable of forming an image having high fastness to an active gas in light and environment, particularly to an ozone gas and to provide an ink jet recording method. <P>SOLUTION: The ink composition using a phthalocyanine compound having a specific structure, particularly ink for ink jet recording and an ink jet recording method are provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ink composition containing a novel phthalocyanine compound, and more particularly to an inkjet recording ink and an inkjet recording method.

[0002]

2. Description of the Related Art In recent years, as an image recording material, a material for forming a color image has been mainly used, and specifically, an ink jet type recording material, a heat transfer type image recording material, and an electrophotographic type recording are used. Materials, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc. are widely used. Also, in the LCD and PDP in the display,
Color filters are used in CCDs and other electronic components in photography equipment. These color image recording materials and color filters use so-called additive color mixture method and subtractive color mixture method of three primary colors (dye or pigment) in order to reproduce or record a full color image. The fact is that there is no robust dye that has absorption characteristics that can be realized and that can withstand various usage conditions.
Improvements are strongly desired.

The ink jet recording method is rapidly spreading and further developing because of low material cost, high speed recording, low noise during recording, and easy color recording. is there. Ink jet recording methods include a continuous method for continuously ejecting droplets and an on-demand method for ejecting droplets according to an image information signal. The ejection method is a droplet that is applied with pressure by a piezo element. There are a method of ejecting liquid, a method of generating bubbles in the ink by heat to eject a droplet, a method of using ultrasonic waves, or a method of sucking and ejecting a droplet by electrostatic force. Further, as the ink for inkjet recording,
Water-based ink, oil-based ink, or solid (melt type) ink is used.

The dye used in such ink jet recording ink has good solubility or dispersibility in a solvent, and high density recording is possible.
Good hue, active gas in light, heat and environment (N
Ox, ozone, and other oxidizing gases such as SOx), robustness against water and chemicals, good fixability to the image receiving material, and less bleeding,
It is required that the ink be excellent in storability, have no toxicity, have high purity, and be inexpensively available. In particular, there is a strong demand for a dye that has a good cyan hue and that is robust against active gases in the light and the environment, particularly, oxidizing gases such as ozone.

As a cyan dye skeleton used in a water-soluble ink for ink jet recording, phthalocyanine type and triphenylmethane type are typical. Typical phthalocyanine dyes which have been reported and used most widely include phthalocyanine derivatives classified into the following 1 to 6.

1. Direct Blue 86 or D
irect Blue 199 and the like of a copper phthalocyanine dye [for _{example, Cu-Pc- (SO 3 Na} ) m: a mixture of m = 1 to 4]

2. JP-A-62-190273, JP-A-63-28690, JP-A-63-306075, JP-A-63-306076, JP-A-2-131983.
JP-A-3-122171, JP-A-3-20088
No. 3, phthalocyanine dyes described in JP-A 7-138511 Patent etc. _{[e.g., Cu-Pc- (SO 3 Na} ) m (SO
₂ NH ₂ ) _n : a mixture of m + n = 1 to 4]

3. JP-A-63-210175, JP-A-SHO
63-37176, JP-A-63-304071, JP
Kaihei 5-171085, WO 00/08102, etc.
Phthalocyanine dye [e.g., Cu-Pc-
(CO₂H)_m(CONR₁R₂) _n: M + n = 0-4
number〕

4. JP-A-59-30874, JP-A-1
-126381, JP-A-1-190770, JP-A-6-16982, JP-A-7-82499, JP-A-8.
-34942, JP-A-8-60053, JP-A-8-
113745, JP-A-8-310116, JP-A-1
0-140063, JP-A-10-298463, JP-A-11-29729, and JP-A-11-320921.
No., EP173476A2, EP468649A1
No., EP559309A2, EP596383A1
No., DE34111476, US6086955, W
O 99/13009, GB 2341868A and the like, a phthalocyanine dye [for example, Cu-Pc-
(SO ₃ H) _m (SO ₂ NR ₁ R ₂ ) _n : m + n = 0 to 4 and m ≠ 0]

5. JP-A-60-208365, JP-A-61-2772, JP-A-6-57653, JP-A-8
-60052, JP-A-8-295819, JP-A-1
0-130517, JP-A-11-72614, JP-A-11-515047, JP-A-11-515048.
No., EP196901A2, WO 95/29208
No., WO 98/49239, WO 98/4924
0, WO 99/50363, WO 99/673
Phthalocyanine dyes such as those described in No. 34 [eg Cu
_{-Pc- (SO 3 H) l (} SO 2 NH 2) m (SO 2 NR
₁ R ₂ ) _n : l + m + n = 0 to 4]

6. JP 59-22967 A, JP 6
1-185576, JP-A-1-95093, JP-A-3-195783, EP649881A1, WO
00/08101, WO 00/08103, and the like. Phthalocyanine dyes [for example, Cu-Pc- (S
O ₂ NR ₁ R ₂ ) _n : n = 1 to 5]

By the way, the Direct Blue 86 or the Direct Blu which is widely used at present.
The phthalocyanine dye represented by e 199 is characterized in that it is superior in light resistance to generally known magenta dyes and yellow dyes. However,
Phthalocyanine dyes have a greenish hue under acidic conditions and are unsuitable for cyan ink. Therefore, when these dyes are used as a 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 change significantly when the recording material used is acidic paper.

Further, even when oxidizing gases such as nitric oxide gas and ozone, which are often taken up as an environmental problem these days, the color is discolored and erased to have a greenish taste, and at the same time, the printing density is lowered.

On the other hand, for the triphenylmethane type,
The hue is good, but the light resistance and ozone gas resistance are very poor.

In the future, when the field of use expands and it is widely used for exhibits such as advertisements, it is often exposed to light and active gas in the environment, so that it has a particularly good hue, There is a strong demand for dyes and ink compositions that are excellent in light fastness and fastness to active gases in the environment (NOx, oxidizing gases such as ozone, as well as SOx) fastness. However,
It is extremely difficult to search for a cyan dye (for example, a phthalocyanine dye) and a cyan ink that satisfy these requirements at a high level. Heretofore, as a phthalocyanine-based dye imparted with ozone gas resistance, JP-A-3
-103484, JP-A-4-39365, JP-A-20
Although disclosed in each publication such as 00-300309,
At present, it has not been possible to achieve both hue and light and oxidative gas fastness at the same time, and cyan ink has not yet provided a product that sufficiently satisfies the market requirements.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art and achieve the following objects. That is, the object of the present invention is to provide (1) a novel dye having three primary colors that has excellent absorption characteristics with excellent color reproducibility and that has sufficient fastness to light, heat, humidity and active gas in the environment. To provide an ink composition for printing such as inkjet, which contains a dye and gives a colored image or coloring material excellent in hue and fastness, (2) In particular, a good hue can be obtained by using the phthalocyanine dye derivative. Another object of the present invention is to provide an inkjet recording ink and an inkjet recording method capable of forming an image having high fastness to an active gas in light and an environment, particularly an ozone gas in the environment.

[0017]

Means for Solving the Problems The present inventors have studied in detail a phthalocyanine dye derivative having good hue and high light fastness and gas fastness (especially ozone gas). It was found that the above problems can be solved by the phthalocyanine compound represented by the following general formula (I) having a dye structure of (a specific substituent species is introduced at a specific substitution position and a specific number of substituents), and the present invention is completed. Came to. That is, according to the present invention, an ink composition, an inkjet recording ink, an inkjet recording method, and a phthalocyanine compound having the following configurations are provided,
The above object of the present invention is achieved.

1. An ink composition comprising a phthalocyanine compound represented by the following general formula (I).

[0019]

[Chemical 5]

In the general formula (I); X ₁ , X ₂ , X ₃ and X ₄
Are each independently the following general formula (II) to general formula (VI
Represents any of the atomic groups shown in I).

[0021]

[Chemical 6]

[In the above general formula (II); W is -O-,-
S -, - NH -, - NZ 1 -, - CH 2 -, - CHZ
_{2 -, - CZ 3 Z 4} - represents a. t represents 0 or 1. A ₁ and A ₂ are each independently a hydroxyl group, a mercapto group, —OZ ₅ , —SZ ₆ , —NH ₂ , —NHZ ₇ , and —NZ _{8.
Z 9, -CH 3, -CH 2} Z 10, -CHZ 11 Z 12, -CZ
₁₃ Z ₁₄ Z _{15 represents} a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. Z _{1 to} Z ₁₅ are 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,
It represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. In the general formula (III), L is —CH ₂ —, —CHZ.
_{16 -, - CZ 17 Z 18} - represents a. t represents 0 or 1. Z _{16 to} Z ₂₁ have the same meaning as Z _{1 to} Z ₁₅ in formula (II). G represents a quaternary ammonium counter anion. In formula (IV), B ₁ and B ₂ are each independently -CO.
Z _22, -SOZ _23, represents the -SO ₂ Z ₂₄ or a substituted or unsubstituted heterocyclic group. Z _{22 to} Z ₂₄ are represented by general formula (II)
The same meaning as Z ₁ to Z ₁₅ in. In the general formula (V); Z ₂₅ has the same meaning as Z _{1 to} Z ₁₅ in the general formula (II). In the general formula (VI); Z ₂₆ and Z ₂₇ are each Z ₁ in the general formula (II).
~ Synonymous with Z ₁₅ . In the general formula (VII), Q represents a carbon atom or a nitrogen atom, and D represents an atomic group necessary for forming a 5- or 6-membered heterocycle (which may form a condensed ring with another ring). Represent ] Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a 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, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group,
It represents a heterocyclic thio group, a phosphoryl group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent. However, X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ ,
At least one of Y ₃ and Y ₄ has an ionic hydrophilic group as a substituent. a _{1 to} a ₄ and b _{1 to} b ₄ represent the numbers of X _{1 to} X ₄ and Y _{1 to} Y ₄ , respectively, and are 0 to 4 respectively.
Represents the integer. a ₁ and b ₁ satisfy a ₁ + b ₁ = 4. The same applies to a _{2 to} a ₄ and b _{2 to} b ₄ . However,
All of a _{1 to} a ₄ are never 0 at the same time. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

2. 2. The ink composition according to the above 1, wherein the phthalocyanine compound represented by the general formula (I) has a higher oxidation potential than 1.0 V (vsSCE). 3. The phthalocyanine compound represented by the general formula (I) is
3. The ink composition as described in 1 or 2 above, which is a phthalocyanine compound represented by the following general formula (VIII).

[0024]

[Chemical 7]

In the general formula (VIII), Y _{11 to} Y ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, 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, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group , Acyl group or ion It represents a hydrophilic group. These groups are
Further, it may have a substituent. X _{1 to} X ₄ have the same meaning as in claim 1. However, at least one of X _{1 to} X ₄ and Y _{11 to} Y ₁₈ has an ionic hydrophilic group as a substituent. a _{1 to} a ₄ each independently represent an integer of 0 to 2. However, a ₁ ~a ₄ all are not 0 at the same time. M has the same meaning as in formula (I).

4. 4. The ink composition as described in 3 above, wherein the phthalocyanine compound represented by the general formula (VIII) is a phthalocyanine compound represented by the following general formula (IX).

[0027]

[Chemical 8]

In the general formula (IX), X _{1 to} X ₄ , a _{1 to} a ₄ and M have the same meaning as in the general formula (VIII). However, X
_At least one of _{1 to} X ₄ has an ionic hydrophilic group as a substituent.

5. The phthalocyanine compound represented by the general formula (IX), wherein the ionic hydrophilic group is a carboxyl group, a phosphono group, a sulfo group or a quaternary ammonium group. 6. An inkjet recording ink containing the ink composition according to any one of 1 to 5 above.

7. An ink jet recording method for recording an image on an image receiving material by ejecting ink droplets on an image receiving material having an image receiving layer containing white inorganic pigment particles on a support according to a recording signal. An ink jet recording method comprising:

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. [Phthalocyanine compound] In the present invention, in order to reduce the reactivity with ozone, which is an electrophile, an electron withdrawing group is introduced into the phthalocyanine skeleton to increase the oxidation potential to 1.00 V (vs.
It is preferable to be more precious than SCE). The more preferable the oxidation potential is, the more preferable the oxidation potential is 1.05 V (vs S
More preferred than CE), 1.10V
Those more noble than (vs SCE) are most preferred.

The present inventors have studied the ozone gas fastness of a colored image. As a result, there is a correlation between the oxidation potential of the compound used for the colored image and the ozone gas fastness, and the oxidation potential value is a saturated calomel electrode (SCE). ) For 1.0
It has been found that the ozone gas fastness is further improved by using a phthalocyanine compound which is more noble than V.

The reason why the ozone gas fastness of the colored image is improved can be explained by the relationship between the compound and the ozone gas HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital). That is, it is considered that the coloring compound is oxidized by the reaction between HOMO of the coloring compound and LUMO of ozone gas, and as a result, the ozone gas fastness of the colored image is reduced. HOMO
To lower the reactivity with ozone gas.

The value of the oxidation potential represents the ease with which electrons are transferred from the sample to the electrode. The larger the value (the higher the oxidation potential is), the harder it is for electrons to transfer from the sample to the electrodes. Indicates difficult. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing the electron-withdrawing group, and the oxidation potential becomes less by introducing the electron-donating group.

The method for measuring the oxidation potential will be described in detail below.
It means the potential at which the compound is an anode in voltammetry and the electron of the compound is abstracted, and it is considered to approximately match the energy level of HOMO in the ground state of the compound.

The oxidation potential value (Eox) can be easily measured by those skilled in the art. For this method, see P.
“New Instrument” by Delahay
Methods in Electrochemist
ry ”(1954 Interscience Pu
published by Blissers) and A. J. Bard et al., "El
electronic chemical methods "(19
80 years, published by John Wiley & Sons) and Akira Fujishima et al., "Electrochemical measurement method" (1984 published by Gihodo Publishing Co.).

The measurement of the oxidation potential will be specifically described.
It The oxidation potential is sodium perchlorate or tetrachlorate tetrachloride.
Dimethy containing supporting electrolytes such as propylammonium
In a solvent such as ruformamide or acetonitrile,
1 x 10 test samples^-Four~ 1 x 10 ^-6mol · dm^-3Concentration of
Dissolve in a
For SCE (saturated calomel electrode) using Larography
It is measured as a value for. Also, the supporting electrolyte and
The medium should be appropriate depending on the oxidation potential and solubility of the test sample.
You can choose. Any supporting electrolyte or solvent that can be used
For the medium, see Aki Fujishima et al., "Electrochemical Measurement Method" (1984
Published by Gihodo Publishing Co., Ltd.) Pages 101-118.

The value of the oxidation potential may deviate by about several tens of mil volts due to the influence of the potential difference between the liquids and the liquid resistance of the sample solution, but it is measured by calibrating with a standard sample (for example, hydroquinone). It is possible to guarantee the reproducibility of the value of the applied potential.

The oxidation potential in the present invention is 0.1 mol.
-In N, N-dimethylformamide containing dm ^-3 tetrapropylammonium perchlorate as a supporting electrolyte (compound concentration is 1 x 10 ^-3 mol dm ^-3 ), SCE (saturated calomel electrode) as a reference electrode A graphite electrode is used as a working electrode, a platinum electrode is used as a counter electrode, and a value measured by direct current polarography is used.

Since the oxidation potential varies depending on the structure of the compound, in order to reduce the reactivity with ozone which is an electrophile, it is better to select a dye structure that originally has a noble oxidation potential because the ozone gas fastness is improved. Not only from the viewpoint, but also from the viewpoint of molecular design, it can be said that an electron-withdrawing group or an electron-donating group can be arbitrarily introduced in order to adjust other fastness, hue, physical properties and the like.

For example, in order to lower the reactivity with ozone, which is an electrophile, it is preferable to introduce an electron-withdrawing group at an arbitrary position in the structure of the compound to make the oxidation potential more noble. Therefore, if the Hammett's substituent constant σp value, which is a measure of the electron withdrawing property or electron donating property of the substituent, is used, the oxidation potential can be made more noble by introducing a substituent having a large σp value.

The Hammett's substituent constant σp value will be described. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
A rule of thumb proposed by P. Hammett, which is widely accepted today. There are σp values and σm values for the substituent constants obtained by the Hammett's rule, and these values can be found in many general textbooks.
JA Dean edited "Lange's Handbook of Chemistry" 12th
Edition (1979 McGraw-Hill) and special edition of "Chemistry Area", 122
Issue, pages 96-103 (1979, Nankodo).

Next, the phthalocyanine compound represented by the following general formula (I) used in the ink composition of the present invention will be described in detail. The ink composition of the present invention contains a phthalocyanine compound represented by the following general formula (I) as a colorant.

[0044]

[Chemical 9]

In the above general formula (I); X ₁ , X ₂ , X
₃ and X ₄ each independently represent one of the atomic groups represented by the following general formulas (II) to (VII).

[0046]

[Chemical 10]

In the above general formula (II), W is --O.
-, - S -, - NH -, - NZ 1 -, - CH 2 -, - CH
Z ₂ − and —CZ ₃ Z ₄ − are preferable, and among them, —O—,
-S -, - NH -, - NZ 1 - are more preferred, particularly preferred is -O -, - NH -, - NZ 1 - a. t
Represents an integer of 0 or 1, and preferably t is 1.

In the above general formula (II), A ₁ and A ₂ are
Independently, a hydroxyl group, a mercapto group, -OZ _5, -
_{SZ 6, -NH 2, -NHZ 7} , -NZ 8 Z 9, -CH 3, -
_{CH 2 Z 10, -CHZ 11 Z} 12, -CZ 13 Z 14 Z 15, a substituted or unsubstituted aryl group, when a substituted or unsubstituted heterocyclic group. More preferably a hydroxyl group, a mercapto _{group, -OZ 5, -SZ 6, -NH} 2, -N
HZ ₇ , -NZ ₈ Z ₉ , most preferably a hydroxyl group,
_{-OZ 5, -NH 2, -NHZ 7} , a -NZ ₈ Z _9. Z ₁
To Z ₁₅ are 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 heterocyclic group is preferable, and a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group are particularly preferable.

In the above general formula (III), L is --CH.₂
-, -CHZ₁₆-, -CZ₁₇Z₁₈− Is preferable,
-CH₂The case of − is more preferable. t is 0 or 1
Is more preferable, but t is more preferably 0. Z₁₆~
Z_{twenty one}Is Z in the general formula (II). ₁~ Z₁₅Synonymous with and preferred
The same applies to the new example. G is quaternary ammonium vs. ani
Indicates ON. Preferred examples of G include halogenio
Ion, sulfate ion, phosphate ion, perchlorate ion, tetra
Fluoroborate ion, hexafluorophosphate ion
Yes, more preferably, a halogen ion, a sulfate ion,
Phosphate ion, preferably halogen ion
is there.

In the above general formula (IV), B ₁ and B ₂ are each independently -COZ ₂₂ , -SOZ ₂₃ , -SO ₂ Z _24.
Alternatively, a substituted or unsubstituted heterocyclic group is preferable.
More preferably, it is —COZ ₂₂ or a substituted or unsubstituted heterocyclic group. Z _{22 to} Z ₂₄ have the same meanings as Z _{1 to} Z ₁₅ in formula (II), and preferred examples are also the same.

In the general formula (V), Z ₂₅ has the same meaning as Z _{1 to} Z ₁₅ in the general formula (II), and preferred examples are also the same.

In the general formula (VI), Z ₂₆ and Z ₂₇ have the same meanings as Z _{1 to} Z ₁₅ in the general formula (II), and preferred examples are also the same.

In the above general formula (VII), Q represents a carbon atom or a nitrogen atom, and D is necessary for forming a 5- or 6-membered hetero ring (which may form a condensed ring with another ring). Represents a group of atoms. The atomic group is preferably composed of carbon atoms and at least one of nitrogen atoms, sulfur atoms and oxygen atoms. Among the heterocycles formed by Q and D, a 5- or 6-membered heterocycle is particularly preferable. Preferred examples of the heterocycle composed of Q and D include imidazole, pyrazole, thiazole, isothiazole, oxazole, pyrrole, pyrazolone,
Indole, isoxazole, thiophene, furan,
Pyran, penthiophene, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, pyridone and the like are included.

D may have a substituent, and the substituent includes a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group and a 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, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl Groups, acyl groups and ions Hydrophilic groups are preferred. These groups may further have a substituent.

Among them, hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, sulfonamide group, carbamoyl group. , A sulfamoyl group, an alkoxycarbonyl group and an ionic hydrophilic group are preferable, and a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group and a cyano group are particularly preferable, and a hydrogen atom is preferable. , An alkyl group, an aryl group, and a heterocyclic group are most preferable. These groups may further have a substituent.

The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group and the like. As the ionic hydrophilic group,
A carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group, the phosphono group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include an alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and an organic cation (eg, Tetramethylguanidinium ion).

Regarding the substituents of X ₁ , X ₂ , X ₃ and X ₄ , at least one is present in each benzene ring of the phthalocyanine, and the total σp value of the substituents of the entire phthalocyanine skeleton is 1.6 or more. It is preferable to introduce.

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group or a hydroxyl group. Group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amido group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, Carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, Acyl group or ionic parent Represents an aqueous group. These groups may further have a substituent. Among them, hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, sulfonamide group,
A carbamoyl group, a sulfamoyl group and an alkoxycarbonyl group are preferable, and particularly a hydrogen atom, a halogen atom,
A cyano group is preferred, and a hydrogen atom is most preferred.

However, X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y
_At least one of ₃ and Y ₄ has an ionic hydrophilic group as a substituent. The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group and the like. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion which forms a salt include alkali metal ions (eg, lithium ion, sodium ion, potassium ion) and organic cations (eg, tetramethyl group). Anidium ion).

Examples of the substituent which Y ₁ , Y ₂ , Y ₃ and Y ₄ can have include the following substituents.
Halogen atom (for example, chlorine atom, bromine atom); C1-C12 straight or branched chain alkyl group, C7
-18 aralkyl group, C2-C12 alkenyl group, C2-C12 linear or branched alkynyl group, C3-C12 cycloalkyl group which may have a side chain, A cycloalkenyl group having 3 to 12 carbon atoms which may have a side chain (as specific examples of the above group, for example, methyl, ethyl, propyl, isopropyl, t-butyl,
2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl); aryl groups (eg phenyl, 4-t-butylphenyl, 2,
4-di-t-amylphenyl); a heterocyclic group (for example,
Imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl); alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy); aryloxy group (for example, , Phenoxy, 2
-Methylphenoxy, 4-t-butylphenoxy, 3-
Nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl); Acylamino group (eg acetamide, benzamide, 4- (3
-T-butyl-4-hydroxyphenoxy) butanamide); alkylamino group (eg, methylamino, butylamino, diethylamino, methylbutylamino); anilino group (eg, phenylamino, 2-chloroanilino; ureido group (eg, phenyl) Ureido, methylureido, N, N-dibutylureido); sulfamoylamino group (for example, N, N-dipropylsulfamoylamino); alkylthio group (for example, methylthio, octylthio, 2-phenoxyethylthio); arylthio group (For example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio);
Alkyloxycarbonylamino group (for example, methoxycarbonylamino); Sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecane); Carbamoyl group (for example, N-ethylcarbamoyl, N, N-) Dibutylcarbamoyl); sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl); sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluene) Sulfonyl); alkyloxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl); heterocyclic oxy group (eg, 1
-Phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy); an azo group (eg, phenylazo,
4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo); acyloxy group (eg acetoxy); carbamoyloxy group (eg N-methylcarbamoyloxy, N-phenyl Carbamoyloxy); silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy); aryloxycarbonylamino group (eg, phenoxycarbonylamino); imide group (eg, N-succinimide, N-phthalimi); heterocyclic thio group ( For example, 2-benzothiazolylthio,
2,4-di-phenoxy-1,3,5-triazole-
6-thio, 2-pyridylthio); sulfinyl group (eg, 3-phenoxypropylsulfinyl); phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl); aryloxycarbonyl group (eg, phenoxycarbonyl) An acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl); an ionic hydrophilic group (eg, carboxyl group, phosphono group, sulfo group, and quaternary ammonium group); other cyano group, hydroxyl group, nitro group , Amino groups and the like.

A₁~ A_Four, B₁~ B_FourAre each X₁~ X_Four
And Y₁~ Y_FourThe number of₁~ A_FourAnd b₁~ B
_FourEach independently represents an integer of 0 to 4. However, a₁
~ A_FourNot all can be 0 at the same time. a₁And b₁
Is a₁+ B₁= 4 is satisfied. a ₂~ A_Four, B₂~ B_FourAbout
The same is true. Note that a₁~ A_FourAnd b₁~ B_FourIs 2 or more
When representing the above integer, multiple X₁~ X_FourAnd Y₁~ Y_FourIs
They may be the same or different.

Particularly preferred is a₁Represents 1 or 2
Then b₁Is a combination that represents 3 or 2, in which
But a₁Represents 1, b₁The combination in which is 3 is the best
Good (A₂, B₂), (A₃, B₃), (A_Four, B_Four)of
In each combination, (a ₁, B₁) And above
Similar combinations are preferred.

M is a hydrogen atom, a metal element, a metal oxide,
Represents a metal hydroxide or metal halide. As the metal element, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta,
Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, P
t, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, S
Preferred examples include n, Pb, Sb and Bi. Of these, Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable.
Preferred examples of the metal oxide include VO and GeO. Metal hydroxides include Si (OH) ₂ , Cr (OH) ₂ , Sn (OH)
_{2 and the} like are preferable. Examples of metal halides include AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl ₂ , GaCl, ZrC.
l and the like.

In the phthalocyanine compound represented by the general formula (I), Pc (phthalocyanine ring) is a dimer (for example, Pc-MLMM-) via L (divalent linking group).
Pc) or a trimer may be formed, and a plurality of Ms present at that time may be the same or different.

The divalent linking group represented by L is an oxy group (-O-), a thio group (-S-) or a carbonyl group (-CO).
-), a sulfonyl group (-SO ₂ -), an imino group (-NH
-), a methylene group (-CH ₂ -), and a group formed by combining these.

Examples of the halogen atom represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ include a fluorine atom, a chlorine atom and a bromine atom.

The alkyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkyl group having a substituent and an unsubstituted alkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms excluding the substituents is preferable.
Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom and an ionic hydrophilic group. Examples of alkyl groups are methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3
-Sulfopropyl and 4-sulfobutyl are included.

The cycloalkyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group has 5 to 12 carbon atoms excluding the substituents.
Is preferred. Examples of the substituent include an ionic hydrophilic group. Examples of cycloalkyl groups include:
A cyclohexyl group is included.

The alkenyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. As the alkenyl group, an alkenyl group having 2 to 12 carbon atoms excluding the substituents is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include vinyl group, allyl group and the like.

The aralkyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms excluding the substituents. Examples of the substituent include an ionic hydrophilic group. Examples of aralkyl groups include benzyl and 2
Includes a phenethyl group.

The aryl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms excluding the substituents 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 is included.

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

The alkylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkylamino group having a substituent and an unsubstituted alkylamino group. The alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms excluding the substituents. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The alkoxy group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group excluding the substituents is preferably an alkoxy group having 1 to 12 carbon atoms. Examples of the substituent include an alkoxy group, a hydroxyl group and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group and a 3-carboxypropoxy group.

The aryloxy group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group has 6 to 12 carbon atoms excluding the substituents.
The aryloxy group of is preferred. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group and an o-methoxyphenoxy group.

The amide group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an amide group having a substituent and an unsubstituted amide group. As the amide group, an amide group having 2 to 12 carbon atoms excluding the substituents is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the amide group include an acetamide group, a propionamide group, a benzamide group and a 3,5-disulfobenzamide group.

The arylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group has 6 to 12 carbon atoms excluding the substituents.
The arylamino group of is preferred. Examples of substituents are:
A halogen atom and an ionic hydrophilic group are included. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

The ureido group represented by Y ₁ , Y ₂ , Y ₃ and Y _{4 includes} a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably an ureido group having 1 to 12 carbon atoms excluding the substituents. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include 3-methylureido group, 3,
A 3-dimethylureido group and a 3-phenylureido group are included.

The sulfamoylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes 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.

The alkylthio group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkylthio group having a substituent and an unsubstituted alkylthio group. As the alkylthio group, an alkylthio group having 1 to 12 carbon atoms excluding the substituents is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

The arylthio group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 12 carbon atoms excluding the substituents. Examples of the substituent include an alkyl group,
And an ionic hydrophilic group. Examples of the arylthio group include a phenylthio group and a p-tolylthio group.

The alkoxycarbonylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. As the alkoxycarbonylamino group, an alkoxycarbonylamino group having 2 to 12 carbon atoms excluding the substituents is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonamide group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group. The sulfonamide group has 1 to 12 carbon atoms excluding the substituents.
The sulfonamide group of is preferred. Examples of the substituent include an ionic hydrophilic group. Examples of sulfonamide groups include:
Includes methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

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

The sulfamoyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of substituents include:
An alkyl group and an aryl group are included. Examples of sulfamoyl groups include dimethylsulfamoyl group and di- (2-
A hydroxyethyl) sulfamoyl group and a phenylsulfamoyl group are included.

The alkoxycarbonyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms excluding the substituents is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

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

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

The acyloxy group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an acyloxy group having a substituent and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 12 carbon atoms excluding the substituents is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

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

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

The aryloxycarbonyl group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group,
An aryloxycarbonyl group having 7 to 12 carbon atoms excluding the substituents is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The aryloxycarbonylamino group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms excluding the substituents. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

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

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

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

The acyl group represented by Y ₁ , Y ₂ , Y ₃ and Y 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 excluding the substituents 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 ionic hydrophilic group represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a sulfo group, a carboxyl group, a phosphono group,
And quaternary ammonium groups and the like. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion which forms a salt include alkali metal ions (eg, lithium ion, sodium ion, potassium ion) and organic cations (eg, tetramethyl group). Anidium ion).

The alkyl group represented by Z _{1 to} Z ₂₇ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms excluding the substituents. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom and an ionic hydrophilic group. Examples of alkyl groups include methyl, ethyl, butyl, n-propyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

The cycloalkyl group represented by Z _{1 to} Z ₂₇ includes
A cycloalkyl group having a substituent and an unsubstituted cycloalkyl group are included. As the cycloalkyl group, a cycloalkyl group having 5 to 12 carbon atoms excluding the substituents is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by Z _{1 to} Z ₂₇ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. As the alkenyl group, an alkenyl group having 2 to 12 carbon atoms excluding the substituents is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include vinyl group, allyl group and the like.

The aralkyl group represented by Z _{1 to} Z ₂₇ is
The aralkyl group having a substituent and the unsubstituted aralkyl group are included. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms excluding the substituents. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by Z _{1 to} Z ₂₇ includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms excluding the substituents is preferable. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl, m-sulfophenyl.
Examples of the substituent include an alkyl group (R-), an alkoxy group (RO-), an alkylamino group (RNH-, RR'N).
-), Carbamoyl group (-CONHR), sulfamoyl group (-SO ₂ NHR), sulfonylamino group (-NH
SO ₂ R), a halogen atom, and an ionic hydrophilic group are included (the above R and R ′ represent an alkyl group and a phenyl group, and these may further have an ionic hydrophilic group).

The heterocyclic group represented by Z _{1 to} Z ₂₇ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group,
Further, it may form a condensed ring with another ring. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group. The heterocyclic group may form a condensed ring with another ring. Examples of the heterocyclic group include, without limitation, the substitution position of the heterocycle, each independently being imidazole,
Benzimidazole, pyrazole, benzopyrazole,
Triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, oxazole, benzoxazole, thiadiazole, pyrrole, benzopyrrole, indole, isoxazole, benzisoxazole, thiophene, benzothiophene, furan,
Examples include benzofuran, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, cinnoline, phthalazine, quinazoline, quinoxaline, triazine and the like. Examples of the substituent include an alkyl group (R-), an alkoxy group (RO-), an alkylamino group (RNH-, RR ').
N-), carbamoyl group (-CONHR), sulfamoyl group (-SO ₂ NHR), sulfonylamino group (-N
HSO ₂ R), a halogen atom, and an ionic hydrophilic group are included (the above R and R ′ represent an alkyl group and a phenyl group, and these may further have an ionic hydrophilic group).

When the phthalocyanine dye represented by the general formula (I) is water-soluble, it preferably has an ionic hydrophilic group. The ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group and the like. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, the phosphono group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion,
And sodium cations, potassium ions) and organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, an alkali metal salt is preferable, and a lithium salt is particularly preferable because it enhances the solubility of the dye and improves the ink stability. The number of ionic hydrophilic groups is at least 2 per molecule of phthalocyanine dye.
Those having one or more are preferable.

Regarding the preferred combination of the substituents of the compound represented by formula (I), the compound in which at least one of the various substituents is the above-mentioned preferred group is preferable, and more various substituents are preferable. The compound having the preferable groups is more preferable, and the compound having all the substituents as the preferable groups is most preferable.

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

[0108]

[Chemical 11]

In the above general formula (VIII), X _{1 to} X
₄ are each independently X _{1 to} X ₄ in the general formula (I).
And the preferred examples are also the same.

Y _{11 to} Y ₁₈ each independently have the same meaning as Y ₁ , Y ₂ , Y ₃ and Y _{4 in} formula (I), and the preferred examples are also the same.

A _{1 to} a ₄ each independently represents a number from 0 to 2 (provided that all of a _{1 to} a ₄ do not become 0 at the same time), and preferably 4 ≦ a ₁ + a ₂ + a ₃ Represents a number of 1 or 2 which satisfies + a ₄ ≦ 8, more preferably 4 ≦ a
₁ + a ₂ + a ₃ + a ₄ ≦ 6 is satisfied, and most preferably, each is 1 (a ₁ = a ₂ = a ₃ = a ₄ = 1).

M has the same meaning as M in formula (I), and the preferred examples are also the same.

When the phthalocyanine dye represented by the general formula (VIII) is water-soluble, it preferably has an ionic hydrophilic group. The ionic hydrophilic group includes a sulfo group,
A carboxyl group, a phosphono group and a quaternary ammonium group are included. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, the phosphono group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counterions, alkali metal salts are preferred,
In particular, a lithium salt is particularly preferable because it enhances dye solubility and ink stability. The number of ionic hydrophilic groups is preferably at least 2 or more in one molecule of the phthalocyanine dye, and particularly preferably at least 2 or more of sulfo group and / or carboxyl group.

Regarding the preferred combination of the substituents of the compound represented by the general formula (VIII), a compound in which at least one of the various substituents is the above-mentioned preferred group is preferable, and more various substituents are preferable. The compounds having the above-mentioned preferable groups are more preferable, and the compounds having all the substituents as the preferable groups are the most preferable.

Among the phthalocyanine compounds represented by the general formula (VIII), the phthalocyanine compound having the structure represented by the general formula (IX) is more preferable. The phthalocyanine compound represented by the general formula (IX) of the present invention is described in detail below.

[0116]

[Chemical 12]

[0117] _{X 1 ~X 4, a 1 ~a} 4 and M have the general formula (VIII) X ₁ ~X ₄ in, a ₁ are each synonymous with ~a ₄ and M, are the preferable examples .

When the phthalocyanine dye represented by the general formula (IX) is water-soluble, it preferably has an ionic hydrophilic group. The ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphono group, a quaternary ammonium group and the like. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, the phosphono group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion,
And sodium cations, potassium ions) and organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, an alkali metal salt is preferable, and a lithium salt is particularly preferable because it enhances the solubility of the dye and improves the ink stability. The number of ionic hydrophilic groups is at least 2 per molecule of phthalocyanine dye.
Those having at least two sulfo groups and / or carboxyl groups are particularly preferable.

Among the phthalocyanine compounds represented by the general formula (IX), particularly preferable combinations of substituents are the same as the particularly preferable combinations of substituents in the general formula (VIII).

Regarding the preferred combination of the substituents of the compound represented by the general formula (IX), a compound in which at least one of the various substituents is the above-mentioned preferred group is preferable, and more various substituents are preferable. The compounds having the above-mentioned preferable groups are more preferable, and the compounds having all the substituents as the preferable groups are the most preferable.

The general formulas (I), (VIII), and
The phthalocyanine compound represented by (IX) will be described in detail. The compounds represented by the general formulas (I), (VIII), and (IX) have specific structures not known in the past (especially,
A novel compound in which a specific number of substituents are introduced into a phthalocyanine mother nucleus at a specific position), and is useful as a water-soluble dye for inkjet and a synthetic intermediate for the water-soluble dye, and a useful chemical compound. -A compound that can serve as an intermediate for pharmaceuticals and agricultural chemicals.

It is generally known to use various phthalocyanine derivatives as an ink composition for ink jet recording. The phthalocyanine derivative represented by the following general formula (X) has an unavoidable substituent R during synthesis.
Substitution position of n (n = 1 to 16) (R ₁ : 1-position to R ₁₆ : 1)
Although it may include isomers (defined as the 6-position herein), these substituted position isomers are often regarded as the same derivative without distinguishing from each other. In addition, when the substituent of R includes isomers, without distinguishing them,
Often regarded as the same phthalocyanine derivative.

[0123]

[Chemical 13]

The case where the structures of the phthalocyanine compounds defined in the present specification are different is described by the general formula (X). When the constituent atomic species of the substituent Rn (n = 1 to 16) are different, the substituent Rn is The number of R is different or the substituent R
This is either case where the position of n is different.

In the present invention, the above general formulas (I) and (VI
II) and (IX) are different in the structure of the phthalocyanine compound (especially at the substitution position), and the following three types are defined and defined.

(1) β-position substitution type: (2 and / or 3
1st, 6th and / or 7th, 10th and / or 11th, 1st
Phthalocyanine compound having a specific substituent at 4- and / or 15-position) (2) α-position substitution type: (specified at 1- and / or 4-position, 5- and / or 8-position, 9- and / or 12-position, 13- and / or 16-position (3) α, β-position mixed substitution type: (phthalocyanine compound having a specific substituent in the 1 to 16-positions without regularity)

In the present specification, when a derivative of a phthalocyanine compound having a different structure (in particular, a different substitution position) is described, the above (1) β-position substitution type, (2) α-position substitution type, (3 ) Use the α, β-position mixed substitution type.

The phthalocyanine derivative used in the present invention is described, for example, by Shirai-Kobayashi, "Phthalocyanine-Chemistry and Function" published by IPC Co., Ltd. (P.1-62),
C. C. Leznoff-A. B. P. Lever co-authored, VCH issue'Phthalocyanines-P
properties and Application
s' (P.1 to 54) and the like, and can be synthesized by quoting or combining methods similar thereto.

General formulas (I), (VIII) and (IX) of the present invention
The phthalocyanine compound represented by is obtained by reacting a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following formula with a metal derivative represented by the general formula (XI). Can be induced. Further, a precursor (compound R) having no substituents represented by the general formulas (II) to (VII) and a metal derivative represented by the general formula (XI) are reacted to once synthesize a phthalocyanine compound, In the subsequent reaction, it is possible to derive the substituent represented by the general formula (II).

[0130]

[Chemical 14]

In each of the above formulas, Xp is the above general formula (I),
(VIII) and (IX) correspond to X ₁ , X ₂ , X ₃ or X ₄ , and Yq and Yq ′ are Y ₁ to
Equivalent to Y ₄ . In addition, in the compound R, Xp ′ represents a group capable of leading the atomic groups of the general formulas (II) to (VII).

General formula (XI): M- (Y) d In general formula (XI), M is the above general formula (I), (VIII),
It is the same as M in (IX), Y represents a monovalent or divalent ligand such as a halogen atom, an acetate anion, acetylacetonate, or oxygen, and d is a number from 1 to 4. General formula (XI)
Examples of the metal derivative represented by are Al, Si, Ti,
V, Mn, Fe, Co, Ni, Cu, Zn, Ge, R
Examples thereof include u, Rh, Pd, In, Sn, Pt, and Pb halides, 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, Examples thereof include manganese acetate, acetylacetone manganese, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride and the like.

The metal derivative and the phthalonitrile compound represented by the compound P and the compound R are used in a molar ratio of 1 :.
It is preferably 3 to 1: 6. The amount of the metal derivative and the diiminoisoindoline derivative represented by the compound Q used is preferably 1: 3 to 1: 6 in terms of molar ratio.

The reaction is usually carried out 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-xanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, Triethylene glycol, polyethylene glycol, I-methoxy-2-propanol, 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 mass, preferably 5 to 20 times by mass that of the phthalonitrile compound.

In the reaction, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or ammonium molybdate may be added as a catalyst. The addition amount is 0.1 to 10 times mol, preferably 0.5 to 2 times mol, per 1 mol of the phthalonitrile compound and / or diiminoisoindoline derivative.

The reaction temperature is 70 to 300 ° C., preferably 7
It is preferably carried out in the reaction temperature range of 0 to 250 ° C, particularly preferably in the reaction temperature range of 70 to 230 ° C. The reaction rate is extremely slow at 60 ° C or lower. Three
If the temperature is higher than 00 ° C, the phthalocyanine compound may be decomposed.

The reaction time is preferably 0.5 to 20 hours, more preferably 0.5 to 15 hours, and particularly preferably 0.5 to 10 hours. preferable. If 0.5 hours or less, a large amount of unreacted raw material is present, and if it is 20 hours or more, the phthalocyanine compound may be decomposed.

The products obtained by these reactions are used as a product after being treated according to a usual post-treatment method for organic synthesis reaction, and then purified or not. That is, for example, the product liberated from the reaction system is not purified, or recrystallization or column chromatography (eg, gel permeation chromatography (SEPHADEX) is performed.
_(TM LH-20: manufactured by Pharmacia) or the like, and the product can be provided as a product by performing an operation of purifying alone or in combination. Further, after the reaction is completed, the reaction solvent is distilled off, or it is poured into water or ice without distillation,
It can be provided as a product after the neutralized or unneutralized liberated product is not purified, or after purification by recrystallization, column chromatography, etc., alone or in combination. . After completion of the reaction, the reaction solvent is distilled off, or the mixture is poured into water or ice without distillation, neutralized or unneutralized, and extracted with an organic solvent / aqueous solution to purify the product. The product can be provided as a product without the use, or after performing an operation of purifying by crystallization or column chromatography alone or in combination.

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

The thus obtained phthalocyanine compound represented by the general formula (IX) (for example: a ₁ = a ₂ = a ₃
= A ₄ = 1) is usually a mixture of compounds represented by the following general formulas (a) -1 to (a) -4, which are isomers at each substitution position.

[0141]

[Chemical 15]

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

The phthalocyanine compound represented by the general formula (I) of the present invention corresponds to the above α, β-position mixed substitution type,
The compounds of the general formulas (VIII) and (IX) have the above-mentioned β-position substitution type (2 and / or 3 position, 6 and / or 7 position, 1
It corresponds to a phthalocyanine compound having a specific substituent at the 0- and / or 11-position, and the 14- and / or 15-position. The α, β-position mixed substitution type compound is a mixture of compounds having different substituent positions and numbers, and the β-position substitution type compound is a mixture of compounds having different substituent positions. In the present invention, in any of the substitution types, it was found that the specific substituent represented by, for example, the general formula (II) is very important for improving the robustness. At a certain position (for example, the β-position substitution type is more preferable than the α, β-position mixed substitution type) (for example, 2 or more and 8 or less per molecule of the phthalocyanine compound and having the general formula (IV (2) and / or 3), (6 and / or 7), (1
A derivative having at least one specific substituent in each group of the 0- and / or 11-position) and the (14- and / or 15-position)} introduced into the phthalocyanine mother nucleus solves the problem of the present invention. It was confirmed that it is an extremely important structural feature as a means. Although the cause of these is not clear in detail, the effect of improving the hue, light fastness, ozone gas resistance, etc. brought about by the structural characteristics of the specific substituents cannot be predicted at all from the prior art. is there.

In the present invention, it is very important that the oxidation potential is nobler than 1.0 V (vs SCE) in any of the substitution types in order to improve the fastness, and one or more chiral compounds are contained in the phthalocyanine compound. It has been found that the inclusion of carbon significantly improves the ink stability, the magnitude of which has never been expected from the prior art. Although the cause is unknown in detail, α, β
The β-position substitution type tended to be obviously superior in hue, light fastness, ozone gas resistance, etc., to the -position mixed substitution type.

Specific examples of the phthalocyanine compound of the present invention are shown in the following Tables 1 to 8 (exemplified compounds 101 to 176) based on the structure of the general formula (X). The phthalocyanine compound used in the present invention is as follows. It is not limited to the example of.

In Tables 1 to 8 below, (R ₁ R ₄ ) (R ₂ R ₃ )
(R ₅ R ₈ ) (R ₆ R ₇ ) (R ₉ R ₁₂ ) (R ₁₀ R ₁₁ ) (R ₁₃
The specific examples of each set of R ₁₆ ) (R ₁₄ R ₁₅ ) are independently and in no particular order.

[0147]

[Table 1]

[0148]

[Table 2]

[0149]

[Table 3]

[0150]

[Table 4]

[0151]

[Table 5]

[0152]

[Table 6]

[0153]

[Table 7]

[0154]

[Table 8]

The compound of the present invention can be used as an ink composition, preferably an image forming ink composition. Examples of the use of the compound of the present invention include image recording materials for forming images, particularly color images. Specifically, thermal transfer type image recording materials such as inkjet recording materials described in detail below are used. , Pressure sensitive recording materials, electrophotographic recording materials, transfer type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink jet recording materials, heat transfer type image recording materials, electrophotographic methods. A recording material, more preferably an inkjet recording material. Also, US Pat.
It can also be applied to a dyeing solution for dyeing various fibers of color filters used in solid-state imaging devices such as LCDs and CCDs described in JP-A-08501 and JP-A-6-35182. The dye of the present invention is used by adjusting physical properties such as solubility and heat transfer property suitable for its use by a substituent. The compound of the present invention can be used in a uniform dissolved state, a dispersed dissolved state such as emulsion dispersion, or a solid dispersed state depending on the system used.

[Inkjet Recording Ink] Next, the inkjet recording ink of the present invention will be described. The inkjet recording ink can be prepared by dissolving and / or dispersing the phthalocyanine compound in a lipophilic medium or an aqueous medium. Preferably,
It is an ink using an aqueous medium. If necessary, other additives are contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, permeation accelerators, UV absorbers, antiseptics, mildew-proofing agents, pH adjusting agents, surface tension adjusting agents, and deodorizing agents. Known additives such as foaming agents, viscosity modifiers, dispersants, dispersion stabilizers, rust preventives and chelating agents can be used. In the case of water-soluble ink, these various additives are added directly to the ink liquid. When the oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after preparation of the dye dispersion, but it may be added to the oil phase or the water phase during the preparation.

The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the inkjet ink at the ink ejection port of the nozzle used in the inkjet recording system.

As the anti-drying agent, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivative, glycerin. , Lower alkyl ethers of polyhydric alcohols such as trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, etc. , 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocycles such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. The above-mentioned anti-drying agents may be used alone or in combination of two or more kinds. These drying inhibitors are contained in the ink in an amount of 10 to 50% by mass.
It is preferable to contain.

The penetration enhancer is preferably used for the purpose of allowing the ink jet ink to better penetrate the paper. As the penetration enhancer, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate and nonionic surfactants can be used. . If these are contained in the ink in an amount of 5 to 30% by mass, there is usually sufficient effect,
It is preferable to use it within the range of the addition amount that does not cause bleeding of printing and paper omission (print through).

The ultraviolet absorber is used for the purpose of improving the storability of images. As a UV absorber, JP-A-58
-185677, 61-190537,
Japanese Patent Laid-Open No. 2-782, Japanese Patent Laid-Open No. 5-97075,
Benzotriazole compounds described in JP-A-9-34057, JP-A-46-2784, JP-A-5-
Benzophenone compounds described in JP-A-194483, U.S. Pat. No. 3,214,463, etc.
8-30492, 56-21141, JP-A-10-88106 and the like, cinnamic acid compounds, JP-A-4-298503 and 8-53342.
No. 7, JP-A 8-239368, and JP-A 10-182.
No. 621, Japanese Patent Publication No. 8-501291, etc., triazine compounds, Research Disclosure No. Compounds described in JP-A No. 24239, stilbene compounds and benzoxazole compounds, which fluoresce by absorbing ultraviolet rays, so-called fluorescent whitening agents can also be used.

The anti-fading agent is used for the purpose of improving the storability of images. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromanes, alkoxyanilines, heterocycles, etc., and metal complexes include nickel. Complex, zinc complex and the like. More specifically, Research Disclosure No.
17643, Item VII, I through J, ibid. 151
62, same No. 62. 18716, page 650, left column, same No. Three
6544, page 527, ibid. 872 of 307105
Page, ibid. Compounds described in the patents cited in 15162 and Japanese Patent Application Laid-Open No. 62-215272, pages 127-
The compounds included in the general formulas of representative compounds and the compound examples described on page 137 can be used.

Antifungal agents include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-
Examples thereof include 1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are 0.02 to 0.02 in the ink.
It is preferable to use 1.00% by mass.

As the pH adjusting agent, the above neutralizing agent (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the inkjet recording ink, the pH adjusting agent has a pH of 6% or less.
10 to 10 is preferably added for summer, and more preferably pH 7 to 10.

Examples of the surface tension adjusting agent include nonionic, cationic or anionic surfactants. The surface tension of the inkjet ink of the present invention is 25 to 70.
mN / m is preferred. Furthermore, 25-60 mN / m is preferable. The viscosity of the inkjet recording ink of the present invention is preferably 30 mPa · s or less. 20 mPas
It is more preferable to adjust to the following. Examples of the surfactant include fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkylsulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl sulfate. Anionic surfactants such as ester salts, polyoxyethylene alkyl ethers,
Nonionic surfactants such as polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and oxyethyleneoxypropylene block copolymer are preferable. In addition, SURFYNOLS (Air Products & Ch), which is an acetylene-based polyoxyethylene oxide surfactant, is used.
(Medicals, Inc.) is also preferably used. Also, N,
Also preferred are amine oxide type amphoteric surfactants such as N-dimethyl-N-alkylamine oxide. Furthermore,
Research Disclosure No. pp. 37-38, JP-A-59-157,636. 308119 (1989
It is also possible to use those listed as the surfactants described in (Year).

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

When the phthalocyanine compound of the present invention is dispersed in an aqueous medium, JP-A No. 11-286637 and Japanese Patent Application No. 2000-
No. 78491, No. 2000-80259, No. 2000-62370, etc., as described in JP-A No. 2000-784, the colored fine particles containing a dye and an oil-soluble polymer are dispersed in an aqueous medium.
54, 2000-78491, 2000-203856, 2000-2038
It is preferable to disperse the compound of the present invention dissolved in a high boiling point organic solvent in an aqueous medium as described in each specification of No. 57. The specific method for dispersing the compound of the present invention in an aqueous medium, the oil-soluble polymer used, the high-boiling organic solvent, the additive and the amount thereof are preferably those described in the above patent publications and the like. be able to. Alternatively, the phthalocyanine compound may be dispersed as a solid in a fine particle state. At the time of dispersion, a dispersant or a surfactant can be used. As a dispersing device, a simple stirrer or impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) A specific commercially available device is a Gohlin homogenizer, microfluidizer, DeBEE2000, etc.). Regarding the method for preparing the above ink jet recording ink, in addition to the above-mentioned patent, JP-A-5-14
No. 8436, No. 5-295312, No. 7-97541
No. 7-82515, No. 7-118584, No. 11-286637, and Japanese Patent Application No. 2000-87539, the details of which are also used for preparing the ink jet recording ink of the present invention. it can.

As the aqueous medium, a mixture containing water as a main component and, if desired, a water-miscible organic solvent added thereto can be used. Examples of the water-miscible organic solvent include alcohols (for example, 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) is included. The water-miscible organic solvent may be used in combination of two or more kinds.

Inkjet recording ink 10 of the present invention
It is preferable that the phthalocyanine compound is contained in an amount of 0.2 parts by mass or more and 10 parts by mass or less in 0 parts by mass. Further, in the inkjet ink of the present invention, other dyes may be used in combination with the phthalocyanine compound. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

The ink jet recording ink of the present invention comprises
The viscosity is preferably 40 cp or less. The surface tension is preferably 20 mN / m or more and 70 mN / m or less. Viscosity and surface tension include various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, ultraviolet absorbers, antioxidants, anti-fading agents, anti-mold agents, rust inhibitors. It can be adjusted by adding a dispersant and a surfactant.

The ink jet recording ink of the present invention comprises
It can be used for full-color image formation as well as single-color image formation. To form a full-color image,
A magenta color tone ink, a cyan color tone ink, and a yellow color tone ink can be used, and a black color tone ink may be further used to adjust the color tone.

Any applicable yellow dye can be used. For example, an aryl or heterylazo dye having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, and open-chain active methylene compounds as a coupling component (hereinafter referred to as a coupler component); for example, a coupler component Azomethine dyes having open-chain type active methylene compounds and the like; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dyes Examples of the seed include quinophthalone dye, nitro / nitroso dye, acridine dye, acridinone dye and the like.

Any magenta dye can be used as the applicable magenta dye. For example, aryl or heterylazo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example, arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc.,
Examples thereof include condensed polycyclic dyes such as dioxazine dyes.

Any applicable cyan dye can be used. For example, aryl or heterylazo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having phenols, naphthols, heterocycles such as pyrrolotriazole as coupler components, cyanine dyes, oxonol dyes Examples thereof include polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

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

[Inkjet recording method] In the inkjet recording method of the present invention, energy is applied to the inkjet recording ink so that a known image receiving material, that is, plain paper or resin coated paper, for example, JP-A-8-169172, is disclosed. No. 8-27693, No. 2-276670, No. 7-276789, No. 9-323475, No. 62-23878, No. 10-
No. 153989, No. 10-217473, No. 10-235995, No. 10-337947, No. 10-21797, No. 10-33794.
An image is formed on inkjet-dedicated paper, film, electrophotographic co-paper, cloth, glass, metal, porcelain, etc. described in Japanese Patent Publication No.

When forming an image, a polymer fine particle dispersion (also referred to as polymer latex) may be used together for the purpose of imparting glossiness, water resistance and improving weather resistance. The polymer latex may be applied to the image receiving material before, after, or at the same time as the application of the colorant, so that the place of addition is also in the image receiving paper, It may be in the ink or may be used as a liquid substance of the polymer latex alone.
Specifically, Japanese Patent Application Nos. 2000-363090 and 200
0-315231, 2000-354380, 2000-343944, 2000-268952.
Issue 2000-299465 Issue 2000-297
The method described in each specification such as 365 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. Supports for recording paper and recording film include chemical pulp such as LBKP and NBKP, GP, PGW, RMP, TMP, CTMP, CM.
P, CGP, etc. mechanical pulp, DIP, etc. waste paper pulp, etc. Those manufactured by various devices such as a mesh paper machine and a cylinder paper machine can be used. In addition to these supports, any of synthetic paper and plastic film sheet may be used. The thickness of the support is 10 to 250 μm, and the basis weight is 10 to 250 μm.
250 g / m ² is desirable. The support may be provided with an ink receiving layer and a back coat layer as it is, or may be provided with a size press or an anchor coat layer with starch, polyvinyl alcohol, etc., and then provided with an ink receiving layer and a back coat layer. Further, the support may be subjected to flattening treatment by a calendar device such as a machine calendar, a TG calendar and a soft calendar. In the present invention, a paper and a plastic film, both surfaces of which are laminated with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof), are more preferably used as the support. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a tinting dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support is
It 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 thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. 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, either silicic anhydride obtained by the dry production method or hydrous silicic acid obtained by the wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

As the aqueous binder contained in the ink receiving layer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyalkylene oxide, polyalkylene oxide derivative. Water soluble polymer such as styrene butadiene latex,
Examples thereof include water-dispersible polymers such as acrylic emulsion. These aqueous binders can be used alone or in combination of two or more. In the present invention, among them, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peeling resistance of the ink receiving layer. The ink-receiving layer contains a mordant, a water-proofing agent, a light resistance improver, in addition to the pigment and the aqueous binder.
Surfactants and other additives can be contained.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used. Regarding the polymer mordant, JP-A-48-28325 and JP-A-54-74430 are used.
No. 54-124726, No. 55-22766,
No. 55-142339, No. 60-23850, No. 6
0-23851, 60-2852, 60-2
3853, 60-57836, 60-6064.
No. 3, No. 60-118834, No. 60-122940
No. 60-122941, No. 60-122942
No. 60-235134, JP-A-1-161236.
Publications, US Pat. Nos. 2,484,430 and 25,485.
No. 64, No. 3148061, No. 3309690, No. 4115124, No. 4124386, No. 41938.
No. 00, No. 4273853, No. 4282305, and No. 4450224. JP-A-1-
An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-161236 is particularly preferable. When the polymer mordant described in the publication is used, an image with excellent image quality can be obtained and the light resistance of the image can be improved.

The waterproofing agent is effective for waterproofing the image,
A cationic resin is particularly preferable as the water-proofing agent. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica and the like, and among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably 1 to 15% by mass, and particularly 3 to 3% by mass based on the total solid content of the ink receiving layer.
It is preferably 10% by mass.

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

The surfactant is a coating aid, a peelability improver,
Functions as a slipperiness improver or antistatic agent. The surfactant is described in JP-A-62-173463 and JP-A-62-183457. An organic fluoro compound may be used instead of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil) and a solid fluorine compound resin (for example, tetrafluoroethylene resin). For organic fluoro compounds, see Japanese Patent Publication No. 57-
No. 9053 (columns 8 to 17), JP-A-61-21994.
And No. 62-135826. Other additives added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, optical brighteners, preservatives,
Examples thereof include pH adjusters, matting agents, hardeners and the like. In addition,
The ink receiving layer may be one layer or two layers.

A back coat layer may be provided on the recording paper and the recording film, and 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, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite,
Examples thereof include white inorganic pigments such as hydrolyzed halloysite, magnesium carbonate and magnesium hydroxide, organic pigments such as styrene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins and melamine resins.

Examples of the aqueous binder contained in the back coat layer include styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin. , Water-soluble polymers such as carboxymethyl cellulose, hydroxyethyl cellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the back coat layer include a defoaming agent, a defoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water resistance agent.

Polymer latex may be added to the constituent layers (including the back coat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. Regarding the polymer latex, JP-A Nos. 62-245258 and 62-
It is described in each publication of 13166648 and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking or curling of the layer can be prevented. Curling can also 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 system, and is a known system, for example, a charge control system for ejecting ink by utilizing electrostatic attraction, or a drop-on-demand system utilizing vibration pressure of a piezo element. Method (pressure pulse method), an electric signal is converted into an acoustic beam to irradiate the ink, the acoustic inkjet method of ejecting the ink by utilizing radiation pressure, and the ink is heated to form bubbles,
It is used in a thermal ink jet system or the like that utilizes the generated pressure. The inkjet recording method uses a method of ejecting a large number of low density inks called photo ink in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue but different densities, and a colorless transparent ink. Method is included.

[0188]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.

(Synthesis Example) In the following, the method for synthesizing the phthalocyanine dye derivative of the present invention will be described in detail with reference to Examples, but the starting material, the dye intermediate and the synthesis route are not limited.

The representative phthalocyanine compound of the present invention can be derived, for example, from the following synthetic route.

[0191]

[Chemical 16]

1-1. Synthesis of Compound 1 (Synthesis of 4-aminophthalonitrile) 20.0 g (0.12 mo) in 410 mL of methanol
l) 4-nitrophthalonitrile (manufactured by Aldrich),
90 mL of concentrated hydrochloric acid was added and heat was applied until reflux. Thereto, 20.5 g of iron powder was dividedly added over 50 minutes. Three
After continuing the reflux for 0 minutes, the mixture was filtered through Celite to remove iron powder. The filtrate was cooled to room temperature, and the precipitated solid was collected by filtration. This solid was recrystallized from benzene. 13.40g
(78%)

1-2. Synthesis of compound 2 2,6-dichloro-3-cyano-4-methylpyridine 2
0.0 g (0.11 mol) and 2,4,6-trimethylaniline 65.0 g (0.48 mol) were used at an internal temperature of 160 ° C.
And stirred for 6 hours. The reaction mixture was mixed with ethyl acetate 60
0 ml was added and stirred for 30 minutes. After separating the insoluble matter by filtration, ethyl acetate was distilled off. Hexane was added to the residue, and the precipitated solid was filtered to obtain 26.8 g of the target compound (yield
65%). m / Z (FABMS; posi) = 384

1-3. Synthesis of Compound 3 (Diazotization of 4-aminophthalonitrile and Coupling) 10.0 g (0.07 mol) of 4-aminophthalonitrile was mixed with a solution of 200 ml of concentrated hydrochloric acid and 500 g of ice, and the reaction solution was kept at 5 ° C. . Sodium nitrite (0.1
5 mL of an aqueous solution of 1 mol) was slowly added dropwise, and then 5
The mixture was stirred at 0 ° C for 1 hour. Subsequently, 26.8 g of Compound 2
A solution of (0.07 mol), 500 g of sodium acetate, 400 ml of glacial acetic acid, and 5 L of water was stirred at 5 ° C, and the above diazo solution was slowly added so that the internal temperature did not exceed 10 ° C.
After stirring at 5 ° C for 3 hours, the precipitate was filtered, the solid was washed with water and dried. Purification was performed by recrystallization (methanol).
33.9 g (90%). m / Z (FABMS; pos
i) = 538

1-4. Synthesis of Compound 4 (Exemplified Compound 14
Synthesis of 9) 33.9 g of Compound 3 in 70 mL of ethylene glycol
(0.06 mol) was added. Heat with stirring,
8.5 g (0.01 mol) of copper chloride was added at an internal temperature of 115 ° C. After 2 hours, 10 mL of concentrated hydrochloric acid was added, and 175 mL of isopropanol was immediately added dropwise. After refluxing for 30 minutes,
Cooled to room temperature. The solid was filtered and rinsed with isopropanol. Then, the above solid was slowly added to 30 mL of chlorosulfonic acid kept at 0 ° C. so that the internal temperature did not exceed 10 ° C. After the addition, the mixture was stirred at an internal temperature of 50 ° C for 1 hour. The reaction mixture was poured into saturated saline. The precipitated solid was filtered off and washed with saturated brine. Then, dissolve in 50 mL of water, heat to 80 ° C., and 125 mL of isopropanol
Was dripped. The precipitated solid was separated by filtration and washed with isopropanol. 7.07 g (28%). (ESI-Mass; cluster trivalent ion, analytical value: 1623.0, calculated value: (1
623.0 × 3-3H) /2=2433.2, theoretical value 2
433.0).

[Synthesis Example of Comparative Compound] 2-1. Synthesis of Comparative Compound 1 Chlorosulfonic acid 1 was placed in a three-necked flask equipped with a cooling tube.
50 mL was added, and 25.0 g of copper phthalocyanine was slowly added in portions with stirring while maintaining a temperature not exceeding 20 ° C. (Because of the heat generation, cooling was carried out at the same time.) Then, the mixture was heated to 100 ° C. for 1 hour, and further heated to 135 ° C. for 1 hour, and kept at the same temperature for 5 hours until the generation of gas was completed. Stir for hours. Then, the reaction solution was cooled to 10 ° C., and then the reaction solution was mixed with 1
The mixture was slowly added to a mixture of 500 mL of saturated saline and 500 g of ice to precipitate blue crystals of the target substance. The temperature in the suspension is 0-5 by the supplemental addition of ice.
It was kept at ℃. After further stirring at room temperature for 1 hour, the mixture was filtered through a Nutsche and washed with 1000 mL of cold saturated saline. The obtained solid was dissolved in 700 mL of 0.1 M sodium hydroxide aqueous solution. The solution was heated to 80 ° C. with stirring and stirred at the same temperature for 1 hour. After removing the dust from the aqueous solution while hot, the filtrate is stirred and sodium chloride 270 m
L was gradually added for salting out. The salting-out liquid was heated to 80 ° C. with stirring and stirred at the same temperature for 1 hour. After cooling to room temperature, the precipitated crystals were filtered off, and 150 mL of 2
It was washed with 0% saline. 80% ethanol 2
The obtained crystals were added to 00 mL and stirred under reflux for 1 hour,
After cooling to room temperature, the precipitated crystals were filtered, and further 6
The obtained crystal was added to 200 mL of 0% ethanol aqueous solution, stirred under reflux for 1 hour, cooled to room temperature, and the precipitated crystal was filtered, washed with 300 mL of ethanol and dried to give 34.2 g of the following comparative compound. 1 was obtained as blue crystals. λmax: 624.8 nm; εmax = 3.40 × 1
0 ⁴ ; λmax: 663.8 nm; εmax = 3.57 ×
10 ⁴ (in aqueous solution). As a result of analyzing the obtained compound,
The phthalocyanine copper (II) -substitution position defined in the present specification is a phthalocyanine copper (II) -substitution position of α, β-mixed type, and the sulfo group substitution number ratio is about 4: 3: 2 = 1:
3: 1 mixture (ESI-MS)} was confirmed.

2-2. Synthesis of Comparative Compound 2 Chlorosulfonic acid 1 was placed in a three-necked flask equipped with a cooling tube.
50 mL was added, and 25.0 g of copper phthalocyanine was slowly added in portions with stirring while maintaining a temperature not exceeding 20 ° C. (Because of the heat generation, cooling was carried out at the same time.) Then, the mixture was heated to 100 ° C. for 1 hour, and further heated to 135 ° C. for 1 hour, and kept at the same temperature for 5 hours until the generation of gas was completed. Stir for hours. Then, the reaction solution was cooled to 10 ° C., and then the reaction solution was mixed with 1
The mixture was slowly added to a mixture of 500 mL of saturated saline and 500 g of ice to precipitate blue crystals of the target substance. The temperature in the suspension is 0-5 by the supplemental addition of ice.
It was kept at ℃. After further stirring at room temperature for 1 hour, the mixture was filtered through a Nutsche and washed with 1000 mL of cold saturated saline. The obtained solid was dissolved in 700 mL of 0.1 M aqueous ammonia. The solution was heated to 80 ° C. with stirring and stirred at the same temperature for 1 hour. After the aqueous solution was filtered while removing dust when hot, 270 mL of sodium chloride was gradually added to the filtrate while stirring for salting out. While stirring the salting-out solution,
The mixture was heated to ℃ and stirred at the same temperature for 1 hour. After cooling to room temperature, the precipitated crystals were filtered and washed with 150 mL of 20% saline. Continuously, 80% ethanol 200m
The obtained crystal was added to L, stirred under reflux for 1 hour, cooled to room temperature, the precipitated crystal was filtered, and further the obtained crystal was added to 200 mL of 60% ethanol aqueous solution, and stirred under reflux for 1 hour, After cooling to room temperature, the precipitated crystals were filtered, washed with 300 mL of ethanol, and dried to give 34.
2 g of the following comparative compound 3 was obtained as blue crystals. λmax
: 624.8 nm; εmax = 3.40 × 10 ⁴ ; λma
x: 663.8 nm; εmax = 3.57 × 10 ⁴ (in aqueous solution). As a result of analyzing the obtained compound, the phthalocyanine copper (II) -substitution position defined in the present specification is phthalocyanine copper (II) -substitution position is α, β-mixed type, and the sulfo group substitution number ratio is about 4 pieces: 3 pieces: 2 pieces = 1: 3: 1
Was confirmed to be a mixture (ESI-MS)}.

2-3. Synthesis of comparative compound 3 Nitrobenzene 10 was placed in a three-necked flask equipped with a cooling tube.
0 mL was added, and the temperature was raised to 180 ° C. over 1 hour, and 43.2 g of 4-sulfophthalic acid monosodium salt, 4.7 g of ammonium chloride, 58 g of urea, 0.68 g of ammonium molybdate, and copper (II) chloride 6. 93 g was added, and the mixture was stirred at the same temperature for 6 hours. After cooling the reaction solution to 40 ° C., 200 mL of heated methanol at 50 ° C. was injected, and the resulting solid was crushed and stirred at room temperature for 1 hour. The resulting dispersion is filtered through a Nutsche, 400 mL
Washed with methanol. Subsequently, 1000 mL of a 1 M hydrochloric acid aqueous solution saturated with sodium chloride was added to the obtained solid and boiled to dissolve out unreacted copper salt. After cooling, the precipitated solid was filtered through a Nutsche and washed with 100 mL of 1 M hydrochloric acid saturated saline solution. The obtained solid was dissolved in 700 mL of 0.1 M sodium hydroxide aqueous solution. The solution was heated to 80 ° C. with stirring and stirred at the same temperature for 1 hour. After the aqueous solution was filtered while removing dust when hot, 270 mL of sodium chloride was gradually added to the filtrate while stirring for salting out. The salting-out liquid was heated to 80 ° C. with stirring and stirred at the same temperature for 1 hour. After cooling to room temperature, the precipitated crystals were filtered and washed with 150 mL of 20% saline. Subsequently, the obtained crystal was added to 200 mL of 80% ethanol, stirred under reflux for 1 hour, cooled to room temperature, the precipitated crystal was filtered, and further 60% ethanol aqueous solution 20
The crystal obtained was added to 0 mL, the mixture was stirred under reflux for 1 hour, cooled to room temperature, and the precipitated crystal was filtered to remove ethanol 3
The crystals were washed with 00 mL and dried to obtain 29.25 g of blue crystals. λmax: 629.9 nm; εmax = 6.1
1 × 10 ⁴ (in aqueous solution). The obtained compound was analyzed (mass spectrometry: measured by various instrumental analysis methods such as ESI-MS, elemental analysis and neutralization titration), and as a result, the phthalocyanine copper (II) -substituted position defined in the present specification was β-position substitution type ((2 or 3 position), (6 or 7 position), (10 or 11 position), (14 or 15 position) of each benzene nucleus)
It has one sulfo group and a total of four sulfo groups in one molecule of copper phthalocyanine}.

[0199]

[Chemical 17]

[Example 1] Deionized water was added to the following components to make 1 liter, and the mixture was heated at 30 to 40 ° C for 1 hour.
Stir for hours. Then p with KOH 10 mol / L
H = 9 was prepared and vacuum filtration was performed with a microfilter having an average pore size of 0.25 μm to prepare an ink liquid.

[0201]   Composition of ink liquid A:   6.80 g of the phthalocyanine compound (Exemplary compound 102) of the present invention   Diethylene glycol 10.65g   Glycerin 14.70 g   Diethylene glycol monobutyl ether 12.70g   Triethanolamine 0.65g   Olfin E1010 0.9g

Ink liquids B to E were prepared in the same manner as in ink liquid A, except that the phthalocyanine compound was changed as shown in Table 9 below, and the following compounds were used as ink liquids for comparison. F to H were adjusted. When the dye was changed, it was used so that the addition amount was equimolar to the dye used in the ink liquid A. When two or more dyes were used in combination, they were used in equimolar amounts.

(Image recording and evaluation) The following evaluations were carried out on the ink jet inks of the above-mentioned examples (ink liquids A to E) and comparative examples (ink liquids F to H). The results are shown in Table 9. In Table 9, "color tone",
"Paper dependency", "Water resistance" and "Light resistance" are the same as those for ink jet printers (EP
SON Corp .; PM-700C) photo glossy paper (EPSON PM photo paper <gloss> (KA420PS
K, EPSON) and the image was recorded and then evaluated.

<Paper Dependency> An image formed on a photo glossy paper and a professional photo paper PR101 are separately provided.
The color tone of the image formed by (CANON Co., Ltd .; QBJPRA4) is compared. When the difference between the two images is small, A (good), and when the difference between the two images is large, B (defective),
It was evaluated in two stages.

<Water resistance> The image-formed photo glossy paper was dried at room temperature for 1 hour, immersed in deionized water for 10 seconds, and naturally dried at room temperature, and bleeding was observed. The case without bleeding was evaluated as A, the case with slight bleeding as B, and the case with large bleeding as C.

<Light resistance> The photo glossy paper on which the above image was formed was irradiated with xenon light (85000 lx) for 14 days using a weather meter (Atlas CI65).
Reflection densitometer (X-Rite3)
10TR) and evaluated as the residual dye rate. The reflection density is 1, 1.5 and 2.0.
Measured at points. At any concentration, the case where the residual dye ratio was 70% or more was evaluated as A, 1 or 2 points was less than 70% as B, and the case where all the concentrations were less than 70% was evaluated as C.

<Dark heat storability> The photo glossy paper on which the image was formed was stored as a sample for 7 days under the condition of 80 ° C. and 15% RH, and the image density before and after storage was measured by a reflection densitometer (X-Rite3).
10TR) and evaluated as the residual dye rate. Regarding the residual ratio of dye, the reflection density is 1, 1.5, and 2 of 3
Evaluation was made based on the points, and at any concentration, the dye residual rate was 90% or more, A was given, when the two points were less than 90%, it was given B, and when all the concentrations were less than 90%, it was given C.

<Ozone gas resistance> 5 kV while passing dry air through the double glass tube of the Siemens type ozonizer
An AC voltage is applied and the ozone gas concentration is adjusted to 0.
The photo glossy paper on which the image was formed was left for 14 days in a box set at 5 ± 0.1 ppm, room temperature, and a dark place, and the image density before and after being left under ozone gas was measured by a reflection densitometer (X
-Rite310TR) and evaluated as the residual dye rate. The reflection density was measured at three points of 1.0, 1.5 and 2.0. The ozone gas concentration in the box is measured by the APPLICS ozone gas monitor (model: O
ZG-EM-01). A, 1 or 2 points are 70 when the residual dye rate is 70% or more at any concentration.
Evaluation was made in three stages, with less than% as B, and less than 70% as C at all concentrations.

<Ink storage stability> The solubility of the dye was evaluated by conducting a storage stability test and a clogging recovery property on the ink. Ink storage stability is determined by placing the ink liquids A to K in a polyethylene container and keeping it at −15 ° C. under 2
After storing for 4 hours, subsequently store under conditions of 60 ° C. for 24 hours; −15 ° C. (24 hr.) → 60 ° C. (24 h
r. The above procedure was repeated 10 times to examine the presence or absence of insoluble matter precipitation before and after storage, and the following criteria were evaluated.

[Judgment Criteria] The recording liquid after the passage of time was put in a test tube and visually observed. ◯: Insoluble matter is not observed at all. Δ: A small amount of insoluble matter was observed. X: Insoluble matter is conspicuous and not in a practical level.

<Recovery from clogging> From the number of cleaning operations required until all nozzles eject normally after the printer is filled with each ink and left in an environment of 40 ° C for one month without a cap. The following criteria were evaluated.

[Criteria] A: Return within 2 cleanings. B: Return after 3 to 5 cleanings. C: Return after 6 or more cleanings. NG: Does not return.

<Solubility> The dye was mixed with 5 ml of distilled water and stirred with a magnetic stirrer for 30 minutes. After stirring, it was confirmed whether the dye was completely dissolved in the solvent. The evaluation was defined as shown below and performed in three stages. 1 g of dye is completely dissolved in 5 ml of solvent …… ○ 1 g of dye is not completely dissolved, but 0.2 g of dye is completely dissolved in 5 ml of solvent …… △ 0.2 g of dye is not completely dissolved in 5 ml of solvent …… ×

[0214]

[Table 9]

As shown in Table 9, the images obtained from the ink liquids A to E have higher toughness than the images obtained from the ink liquids F to H, and in particular, a remarkable difference in ozone gas resistance is recognized. Was given. Further, it was found that the ink liquid prepared by the preparation method of the present invention did not deteriorate the printing due to the precipitation of the low-soluble component even when exposed to severe storage conditions, and was excellent in the ink storage stability and the clogging recovery property.

<Oxidation potential> Regarding the value of oxidation potential, the phthalocyanine compound of the present invention was weighed in the range of 10.0 mg to 25.0 mg, and 0.1 mol · dm ⁻³ of tetrapropylammonium perchlorate was used as a supporting electrolyte. Including N, N-
It was measured by direct current polarography with 5 to 15 ml of dimethylformamide (concentration of dye: about 0.001 mol · dm ⁻³ ). In the polarography device, a carbon (GC) electrode was used as a working electrode, and a rotating platinum electrode was used as a counter electrode. The midpoint of the intersection between the current value and the residual current value was taken as the oxidation potential value (vsSCE). When the oxidation potential was 1.0 or more, the evaluation was ◯, and when it was less than that, it was x.

As is clear from Table 9, the ink-jet ink of the present invention had excellent color tone, small paper dependence, and excellent water resistance, light resistance and ozone resistance. Further, it is clear that the image storability such as light resistance and ozone resistance is excellent, especially the ink storage stability.

[Example 2] Using the same ink prepared in Example 1, an image was printed on the inkjet paper photo glossy paper EX manufactured by Fuji Photo Film Co., Ltd. using the same machine as in Example 1, When the same evaluation was performed, the same results as in Example 1 were obtained.

Example 3 The same ink prepared in Example 1 was used in the ink jet printer BJ-F850 (CA).
Example 1
When the same evaluation as above was performed, the same results as in Example 1 were 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. That is, as an oxidizing gas resistance test method that simulates an outdoor environment that is exposed to oxidizing gas such as automobile exhaust gas and sunlight, H.Iwan
o, et al; Journal of Imaging Science and Technolog
y, 38, 140-142 (1944), relative humidity 80%, hydrogen peroxide concentration 120 ppm, and an oxidation resistance test method using a fluorescent lamp irradiation chamber. The test results are
The result was similar to that of Example 1.

[0221]

According to the present invention, (1) by using a phthalocyanine compound having a specific structure as a colorant,
An ink composition having excellent absorption properties with good color reproducibility and sufficient fastness to active gas in light, heat, humidity and environment, and used for printing ink such as ink jet recording (2) The above ink composition has good long-term storage stability of ink, high dissolution stability of dissolved components, and excellent quick-drying property on recording material without clogging of nozzles. Further, (3) an inkjet ink and an inkjet recording having a good hue by using the above ink composition and capable of forming an image having high fastness to an active gas in light and environment, particularly ozone gas. A method is provided, and further, (4) a method for improving the ozone gas fading resistance of an image recorded matter is provided by utilizing the inkjet recording method described above.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2C056 EA13 FC01                 2H086 BA56                 4J039 BC33 BC40 BC44 BC56 BC60                       EA35 EA37 EA38 EA40 EA44                       GA24

Claims (3)

[Claims] 1. An ink composition comprising a phthalocyanine compound represented by the following general formula (I). [Chemical 1] In the general formula (I); X ₁ , X ₂ , X ₃ and X ₄ each independently represent one of the atomic groups represented by the following general formulas (II) to (VII). [Chemical 2] [In the general formula (II); W is -O-, -S-, -NH
_{-, - NZ 1 -, -} CH 2 -, - CHZ 2 -, - CZ 3 Z 4
Represents-. t represents 0 or 1. A ₁ and A ₂ are each independently a hydroxyl group, a mercapto group, —OZ ₅ , and —S.
_{Z 6, -NH 2, -NHZ 7} , -NZ 8 Z 9, -CH 3, -C
_{H 2 Z 10, -CHZ 11 Z} 12, -CZ 13 Z 14 Z 15, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group. Z _{1 to} Z ₁₅ are 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. Represents a group or a substituted or unsubstituted heterocyclic group. In the general formula (III), L is —CH ₂ —, —CHZ.
_{16 -, - CZ 17 Z 18} - represents a. t represents 0 or 1. Z _{16 to} Z ₂₁ have the same meaning as Z _{1 to} Z ₁₅ in formula (II). G represents a quaternary ammonium counter anion. In formula (IV), B ₁ and B ₂ are each independently -CO.
Z _22, -SOZ _23, represents the -SO ₂ Z ₂₄ or a substituted or unsubstituted heterocyclic group. Z _{22 to} Z ₂₄ are represented by general formula (II)
The same meaning as Z ₁ to Z ₁₅ in. In the general formula (V); Z ₂₅ has the same meaning as Z _{1 to} Z ₁₅ in the general formula (II). In the general formula (VI); Z ₂₆ and Z ₂₇ are each Z ₁ in the general formula (II).
~ Synonymous with Z ₁₅ . In the general formula (VII), Q represents a carbon atom or a nitrogen atom, and D represents an atomic group necessary for forming a 5- or 6-membered heterocycle (which may form a condensed ring with another ring). Represent ] Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a 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, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group,
It represents a heterocyclic thio group, a phosphoryl group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent. However, X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ ,
At least one of Y ₃ and Y ₄ has an ionic hydrophilic group as a substituent. a _{1 to} a ₄ and b _{1 to} b ₄ represent the numbers of X _{1 to} X ₄ and Y _{1 to} Y ₄ , respectively, and are 0 to 4 respectively.
Represents the integer. a ₁ and b ₁ satisfy a ₁ + b ₁ = 4. The same applies to a _{2 to} a ₄ and b _{2 to} b ₄ . However,
All of a _{1 to} a ₄ are never 0 at the same time. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. 2. The ink 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 (VIII). [Chemical 3] In formula (VIII), Y _{11 to} Y ₁₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, Nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amido group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group,
Alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group Represents a heterocyclic thio group, a phosphoryl group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent. X _{1 to} X ₄ have the same meaning as in claim 1. However, at least one of X _{1 to} X ₄ and Y _{11 to} Y ₁₈ has an ionic hydrophilic group as a substituent. a
_{1 to} a ₄ each independently represent an integer of 0 to 2. However, a ₁ ~a ₄ all are not 0 at the same time. M
Is synonymous with the case of general formula (I). 3. The ink composition according to claim 2, wherein the phthalocyanine compound represented by the general formula (VIII) is a phthalocyanine compound represented by the following general formula (IX). [Chemical 4] In the general formula (IX), X _{1 to} X ₄ , a _{1 to} a ₄ and M have the same meaning as in the general formula (VIII). However, at least one of X _{1 to} X ₄ has an ionic hydrophilic group as a substituent.