JP2003003109A - Phthalocyanine compound, colored image-forming composition containing the same, ink, ink for ink jet, method for carrying out ink jet recording and method for improving discoloration due to ozone gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new phthalocyanine compound, ink for ink jet and ink jet recording method capable of forming image excellent in hue, light resistance and ozone gas resistance, and provide various coloring compositions such as an ink sheet in a heat-sensitive recording material excellent in hue and fastness, a color toner for electrophotography and a color filter and exhibit a method for strengthening oxidation resistance of image. SOLUTION: This invention relates to a phthalocyanine compound obtained by substituting at least one position of 1-16 positions with a substituted sulfamoyl group (the substituent group is >=2C, particularly aryl group), a coloring composition obtained by using the compound, ink, particularly for ink jet, an ink jet recording method using the ink and further a method for making image strong under oxidizing environment by utilizing the recording method.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel phthalocyanine compound and a colored image-forming composition containing the compound, particularly an oil-soluble ink for cyan ink jet, an inkjet recording method and an ozone gas fading of an image recorded by the use of inkjet recording. A method for improving resistance.

[0002]

2. Description of the Related Art In recent years, as a colored image forming material, a material for forming a color image has been mainly used, and specifically, an ink jet type recording material, a heat transfer type recording material and an electrophotographic type recording material are used. Recording materials, transfer type silver halide photosensitive materials, printing inks, recording pens and the like are widely used. In addition, color filters are used to record and reproduce color images in imaging devices such as CCDs in photographing equipment and in LCDs and PDPs in displays. These color image recording materials and color filters use dyes (dyes and pigments) of three primary colors of so-called additive color mixing method and subtractive color mixing method in order to reproduce or record a full color image, but a preferable color reproduction range. It is the actual situation that there is no robust dye that has absorption characteristics that can realize the above and can withstand various use conditions and environmental conditions, and improvement is 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. 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. As the inkjet ink, water-based ink, oil-based ink, or solid (melting type) ink is used.

The dyes used in such ink jet inks have good solubility or dispersibility in solvents, high density recording, good hue, light, heat, Active gas in the environment (NO
x, ozone and other oxidizing gases such as SOx), robustness against water and chemicals, good fixability to the image receiving material and difficult to bleed, storage as ink It is required to have excellent properties, be non-toxic, have high purity, and be available at low cost.

In particular, it is a dye which has a good cyan hue and is fast against light, humidity and heat, and in particular, prints on an image receiving material having an ink receiving layer containing porous white inorganic pigment particles. In this case, it is strongly desired that the structure is robust against oxidizing gases such as ozone in the environment.

In color copiers and color laser printers utilizing the electrophotographic method, toners in which a coloring material is dispersed in resin particles are generally widely used. As the performance required for color toner, absorption characteristics that can realize a preferable color reproduction range, especially Overhead Pro
high transparency (transparency), which is a problem when used in an injector (hereinafter referred to as OHP), and various robustness under the environmental conditions used. A toner in which a pigment as a coloring material is dispersed in particles is disclosed in JP-A-62-157051.
No. 62-255956 and JP-A No. 6-118715, these toners are excellent in light fastness, but are insoluble and easily agglomerate, resulting in a decrease in transparency of the coloring layer and a hue of a transmitted color. Change is a problem. On the other hand, a toner using a dye as a coloring material is disclosed in JP-A-3-276161.
No. 7,209,912 and No. 8-123085, these toners, on the contrary, have high transparency.
Although there is no hue change, there is a problem in light resistance.

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

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

The dyes used in each of the above-mentioned applications must have the following properties in common. That is, it has favorable absorption characteristics in terms of color reproducibility, fastness under the environmental conditions used, for example, light resistance, heat resistance, moisture resistance, resistance to oxidizing gases such as ozone, and other chemical resistance fastness such as sulfurous acid gas. And the molar absorption coefficient is high.

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

As a cyan dye skeleton used in an inkjet ink, a dye having a structure of phthalocyanine or triphenylmethane is typical.

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

Direct Blue 86 or Di
copper phthalocyanine compound such as rect Blue 87 [eg, Cu—Pc— (SO ₃ Na) _m : m = 1 to 4 mixture]

[Hereinafter, Pc means a phthalocyanine skeleton].

Direct Blue 199 and Japanese Patent Laid-Open Nos. 62-190273 and 63-28690.
JP-A-63-306075, JP-A-63-306
076, JP-A-2-131983, JP-A-3-12
2171, JP-A-3-200883, JP-A 7-1
Phthalocyanine compounds described in 38511 No., etc. _{[e.g., Cu-Pc- (SO 3 Na} ) m (SO 2 NH 2) n: m +
n = 1 to 4 mixture].

JP-A-63-210175 and JP-A-6-206
3-37176, JP-A-63-304071, JP-A-5-171085, WO 00/08102, and the like. Phthalocyanine dyes [for example, Cu-Pc- (CO ₂
H) _m (CONR ₁ R ₂ ) _n : m + n = 0 to 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-8-1.
No. 13745, JP-A-8-310116, JP-A-10
-140063, JP-A-10-298463, JP-A-11-29729, JP-A-11-320921,
EP173476A2, EP468649A1, E
P559309A2, EP596383A1, DE
3411476, US 6086955, WO 99
/ 13009, GB2341868A and the like, phthalocyanine dyes [eg Cu-Pc- (SO ₃ H)]
_m (SO ₂ NR ₁ R ₂ ) _n : m + n = 0 to 4 and m
≠ 0].

JP-A-60-208365 and JP-A-6-208365
1-2772, JP-A-6-57653, and JP-A-8-
60052, JP-A-8-295819, JP-A-10
-130517, Unexamined-Japanese-Patent No. 11-72614, the special table 11-515047, the special table 11-515048,
EP196901A2, WO 95/29208,
WO 98/49239, WO 98/49240
No., WO 99/50363, WO 99/6733
Phthalocyanine dyes described in No. 4 and the like [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].

JP-A-59-22967 and JP-A-61.
-185576, JP-A-1-95093, JP-A-3
-195783, EP649881A1, WO 0
0/08101, WO 00/08103, and the like, such as phthalocyanine dyes [eg, Cu-Pc- (SO ₂ NR
₁ R ₂ ) _n : n = 1 to 5].

By the way, the Direct Blue 87 or the Direct Bl which is widely used at present.
The phthalocyanine dye represented by ue 199 is characterized by being superior in light resistance to the generally known magenta dye and yellow dye.

However, the phthalocyanine dye has a greenish hue under acidic conditions and is 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 if oxidizing gas such as nitric oxide gas or ozone, which has been often taken up as an environmental problem these days, discolors and decolorizes to a greenish color, and at the same time, the printing density also decreases.

On the other hand, the triphenylmethane dye (or pigment) has a good hue but is very poor in light resistance and ozone gas resistance.

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 and There is an increasing demand for dyes and ink compositions having excellent fastness and fastness to active gases in the environment (oxidizing gases such as NOx and ozone, as well as SOx).

However, the development of cyan dyes (for example, phthalocyanine dyes) and cyan inks that meet these requirements at a high level is difficult, and dyes and inks that satisfy the requirements have not yet been obtained. It is in.

So far, phthalocyanine dyes having ozone gas fading resistance (hereinafter also referred to as ozone gas resistance) have been disclosed in JP-A-3-103484 and JP-A-4-393.
No. 65, JP-A No. 2000-30309, etc. are disclosed, but none of them have yet to achieve both hue and fastness to light and oxidizing gas. We have not yet provided products that fully satisfy the requirements.

[0026]

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. Providing compounds (dyes and pigments), (2) Printing inks such as inkjet, color toners for electrophotography, displays such as LCDs and PDPs, which give colored images and coloring materials with excellent hue and fastness. Provided are various colored compositions such as color filters used in image pickup devices such as CCDs and CCDs. (3) In particular, the use of the phthalocyanine compound derivative has a good hue, and an active gas in light and environment, particularly To provide an inkjet ink and an inkjet recording method capable of forming an image having high robustness against ozone gas, and (4) the inkjet recording method described above. By use,
An object of the present invention is to provide an image fastening method for improving ozone gas fading resistance of an image recorded matter.

[0027]

Means for Solving the Problems The present inventors have studied in detail a phthalocyanine compound derivative having a good hue and high light fastness and gas fastness (especially ozone gas), and as a result, it has been found that a specific phthalocyanine compound derivative which has not been heretofore known. It was found that the above-mentioned problems can be solved by a phthalocyanine compound represented by the following general formula (I) having a dye structure (introduction of a specific substituent group at a specific substitution position and a specific number of substituents), and the present invention is completed. I arrived. That is, the above-mentioned object of the present invention can be achieved by the following means.

1. A colored image forming composition comprising a phthalocyanine compound represented by the following general formula (I).

[0029]

[Chemical 5]

In the general formula (I): R ₁ , R ₄ , R ₅ , R ₈ and R
₉ , R ₁₂ , R ₁₃ and R ₁₆ 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 sulfinyl group, a phosphoryl group, or an acyl group, each of which may further have a substituent. R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅
Each independently represent a hydrogen atom or a substituted sulfamoyl group. However, at least one of R ₂ and R ₃ , R ₆ and R ₇ , R ₁₀ and R ₁₁ , and R ₁₄ and R ₁₅ represents a substituted sulfamoyl group, and four or more substituted sulfamoyl groups are present. At least one of them has a substituent having 2 or more carbon atoms. And R ₁ , R ₂ , R ₃ , R ₄ ,
_{R 5, R 6, R 7} , R 8, R 9, R 10, R 11, R 12, R 13,
The total number of carbon atoms of the substituents represented by R ₁₄ , R ₁₅ and R ₁₆ is 8 or more. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.

2. An ink comprising the colored image-forming composition as described in 1 above.

3. 3. The ink according to the above item 2, wherein the phthalocyanine compound represented by the general formula (I) is a phthalocyanine compound represented by the following general formula (II).

[0033]

[Chemical 6]

In the general formula (II): X₁, X₂, X₃, And X_Four
Are each independently a hydrogen atom, a substituted or unsubstituted
Alkyl group, substituted or unsubstituted aryl group, also substituted
Or unsubstituted cycloalkyl group, substituted or unsubstituted
An alkenyl group, a substituted or unsubstituted aralkyl group,
Alternatively, it represents a substituted or unsubstituted heterocyclic group. Y₁,
Y₂, Y₃, And Y_FourAre each independently replaced or
It represents an unsubstituted aryl group. However, X₁, X₂, X₃,
X_Four, Y₁, Y₂, Y₃And Y_FourAt least one of the
Represents a substituent of a number 2 or more, and X₁, X₂, X₃, X_Four,
Y₁, Y₂, Y ₃And Y_FourThe total number of carbon atoms of the substituents represented by
Is 8 or more. M has the same meaning as M in formula (I).
It l, m, n and p are each independently 1 or 2
Represents an integer.

4. 4. The ink according to the above 3, wherein the phthalocyanine compound represented by the general formula (II) is a phthalocyanine compound represented by the following general formula (III).

[0036]

[Chemical 7]

In the general formula (III): W _{1 to} W ₂₀ 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, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group , Sulfinyl group, phospho It represents a group or an acyl group, each of which may further have a substituent. However, W _{1 to} W ₅ ,
At least one set of each set of W _{6 to} W ₁₀ , W _{11 to} W ₁₅ , and W _{16 to} W ₂₀ is a group having at least one substituent having 2 or more carbon atoms, and W ₁ The total number of carbon atoms of the substituents represented by W ₂₀ is 8 or more. M, l, m, n
And p are M, l, and
It is synonymous with m, n, and p.

5. An inkjet ink, which is the ink according to any one of 2 to 4 above.

6. An ink jet recording method comprising forming an image on the image receiving material having an ink image receiving layer containing white inorganic pigment particles on a support, using the ink according to any one of 2 to 5 or the inkjet ink. .

7. 6. A method for improving ozone gas fading resistance of an image-recorded article, which comprises forming an image using the ink or ink-jet ink according to any one of 2 to 5 above.

8. A phthalocyanine compound represented by the general formula (IV).

[0042]

[Chemical 8]

In the general formula (IV): W _{1 to} W ₂₀ 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, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group , Sulfinyl group, phospho It represents a group or an acyl group, each of which may further have a substituent. However, W _{1 to} W ₅ ,
W _{6 to} W ₁₀ , W _{11 to} W ₁₅ , and W _{16 to} W ₂₀ each independently have a substituent having 2 or more carbon atoms, and W
The total number of carbon atoms of the substituents represented by _{1 to} W ₂₀ is 8 or more. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. l, m, n, and p each independently represent an integer of 1 or 2.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. [Phthalocyanine Dye] First, the phthalocyanine compound represented by the general formula (I) will be described in detail. Since the phthalocyanine compound is oil-soluble, it does not have an ionic hydrophilic group in the molecule.

[0045]

[Chemical 9]

In the general formula (I), R ₁ , R ₄ , R ₅ ,
R ₈ , R ₉ , R ₁₂ , R ₁₃ , and R ₁₆ are each independently
Hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide Group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group,
Alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group , A heterocyclic thio group, a sulfinyl group, a phosphoryl group, or an acyl group, each of which may further have a substituent.

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

R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom or a substituted sulfamoyl group. However, at least one of R ₂ and R ₃ , R ₆ and R ₇ , R ₁₀ and R ₁₁ , and R ₁₄ and R ₁₅ represents a substituted sulfamoyl group, and four or more substituted sulfamoyl groups are present. At least one of the
It has a substituent having 2 or more carbon atoms. And R ₁ , R ₂ ,
_{R 3, R 4, R 5} , R 6, R 7, R 8, R 9, R 10, R 11, R
The total carbon number of the substituents represented by ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ is 8 or more.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
_{R 8, R 9, R 10} , R 11, R 12, R 13, R 14, R 15 and R
_Examples of the substituent that ₁₆ can further have include the following substituents.

A halogen atom (eg, chlorine atom, bromine atom), a linear or branched alkyl group having 1 to 12 carbon atoms,
An aralkyl group having 7 to 18 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a linear or branched alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group which may have a side chain having 3 to 12 carbon atoms, A cycloalkenyl group which may have a side chain having 3 to 12 carbon atoms, more specifically, an alkyl group (for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoro). Each group such as methyl and cyclopentyl), an aryl group (for example, phenyl, 4-t-butylphenyl, 2,
4-di-t-amylphenyl and other groups), heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl,
2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, etc.), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (eg, methoxy, ethoxy, 2-methoxyethoxy) , 2-methanesulfonylethoxy, etc.), aryloxy groups (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, etc.) , An acylamino group (eg, acetamide,
Benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, etc.), alkylamino group (eg, methylamino, butylamino, diethylamino, methylbutylamino, etc.), anilino group (eg, , Phenylamino, 2-chloroanilino, etc.), a ureido group (eg, phenylureido, methylureido, N, N-dibutylureido, etc.),
Sulfamoylamino group (for example, N, N-dipropylsulfamoylamino group), alkylthio group (for example,
Each group such as methylthio, octylthio, 2-phenoxyethylthio, etc.), arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2
-Groups such as carboxyphenylthio), alkyloxycarbonylamino groups (eg, methoxycarbonylamino group), sulfonamide groups (eg, groups such as methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), carbamoyl A group (for example, N-
Each group such as ethylcarbamoyl, N, N-dibutylcarbamoyl) and a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl,
Each group such as N, N-diethylsulfamoyl), sulfonyl group (for example, each group such as methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl, etc.) Each group), a heterocyclic oxy group (for example, 1-phenyltetrazole-
5-oxy, 2-tetrahydropyranyloxy and other groups), azo groups (eg, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-
Each group such as hydroxy-4-propanoylphenylazo), an acyloxy group (for example, acetoxy group), a carbamoyloxy group (for example, each group such as N-methylcarbamoyloxy, N-phenylcarbamoyloxy),
A silyloxy group (for example, each group such as trimethylsilyloxy and dibutylmethylsilyloxy), an aryloxycarbonylamino group (for example, a phenoxycarbonylamino group), an imide group (for example, N-succinimide,
Each group such as N-phthalimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio, etc. ), A sulfylyl group (for example, a 3-phenoxypropylsulfinyl group), a phosphoryl group (for example, each group of phenoxyphosphoryl, octyloxyphosphoryl, and ferrylphosphonyl), an aryloxycarbonyl group (for example, a phenoxycarbonyl group), an acyl group (For example, each group such as acetyl, 3-phenylpropanoyl, benzoyl), an ionic hydrophilic group (for example, a carboxyl group, a sulfo group, a quaternary ammonium group,
Sulfonylsulfamoyl group and acylsulfamoyl group); other cyano group, hydroxyl group, nitro group,
Examples thereof include a carboxyl group and an amino group.

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

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
The alkyl group represented by W ₁ , W ₂ , W ₃ , and W 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 include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl,
Included are groups such as cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The cycloalkyl group represented by R ₁₂ , R ₁₃ and R ₁₆ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. As the cycloalkyl group, a cycloalkyl group having 5 to 12 carbon atoms is preferable. Examples of the cycloalkyl group include a cyclohexyl group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The alkenyl group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group has 2 to 12 carbon atoms.
Alkenyl groups are preferred. Examples of the alkenyl group as the substituent include a vinyl group, an allyl group and the like.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The aralkyl group represented by R ₁₂ , R ₁₃ and R ₁₆ includes a substituted aralkyl group and an unsubstituted aralkyl group. The aralkyl group has 7 to 7 carbon atoms.
Twelve aralkyl groups are preferred. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The aryl group represented by R ₁₂ , R ₁₃ and R ₁₆ 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 is preferable. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom and an alkylamino group. Examples of aryl groups include phenyl, p-tolyl, p-
Methoxyphenyl, o-chlorophenyl and m- (3
-Sulfopropylamino) phenyl.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The heterocyclic group represented by R ₁₂ , R ₁₃ and R ₁₆ 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 heterocyclic group include 2-pyridyl group, 2-thienyl group and 2-furyl group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The alkylamino group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an alkylamino group having a substituent and an unsubstituted alkylamino group. As the alkylamino group, an alkylamino group having 1 to 6 carbon atoms is preferable. Examples of the alkylamino group include a methylamino group and a diethylamino group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The alkoxy group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group has 1 to 12 carbon atoms.
Alkoxy groups are preferred. Examples of the substituent include an alkoxy group and a hydroxyl 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.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The aryloxy group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an aryloxy group having a substituent and an unsubstituted aryloxy group. As the aryloxy group, an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of the substituent include an alkoxy group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group and an o-methoxyphenoxy group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The amide group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an amide group having a substituent and an unsubstituted amide group. The amide group is preferably an amide group having 2 to 12 carbon atoms. Examples of the amide group include an acetamide group, a propionamide group, a benzamide group and a 3,5-disulfobenzamide group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The arylamino group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an arylamino group having a substituent and an unsubstituted arylamino group. As the arylamino group, an arylamino group having 6 to 12 carbon atoms is preferable. Examples of the substituent include a halogen atom. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The ureido group represented by R ₁₂ , R ₁₃ and R ₁₆ 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. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group and a 3-methylureido group.
A phenylureido group is included.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The sulfamoylamino group represented by R ₁₂ , R ₁₃ and R ₁₆ 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.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The alkylthio group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms. Examples of the alkylthio group include a methylthio group and an ethylthio group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The arylthio group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an arylthio group having a substituent and an unsubstituted arylthio group. As the arylthio group, an arylthio group having 6 to 12 carbon atoms is preferable. Examples of the substituent include an alkyl group. Examples of arylthio groups include:
A phenylthio group and a p-tolylthio group are included.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The alkoxycarbonylamino group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The sulfonamide group represented by R ₁₂ , R ₁₃ and R ₁₆ includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group. As the sulfonamide group, a sulfonamide group having 1 to 12 carbon atoms is preferable. Examples of sulfonamide groups include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The carbamoyl group represented by R ₁₂ , R ₁₃ and R ₁₆ 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.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The sulfamoyl group represented by R ₁₂ , R ₁₃ and R ₁₆ includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group and an aryl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group, a di- (2-hydroxyethyl) sulfamoyl group, and a phenylsulfamoyl group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The alkoxycarbonyl group represented by R ₁₂ , R ₁₃ and R ₁₆ 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 is preferable. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The heterocyclic oxy group represented by R ₁₂ , R ₁₃ and R _{16 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.
Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The azo group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an azo group having a substituent and an unsubstituted azo group. Examples of the azo group include a p-nitrophenylazo group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The acyloxy group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an acyloxy group having a substituent and an unsubstituted acyloxy group. An acyloxy group has 1 carbon atom
-12 acyloxy groups are preferred. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The carbamoyloxy group represented by R ₁₂ , R ₁₃ and R ₁₆ includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of substituents include:
Alkyl groups are included. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The silyloxy group represented by R ₁₂ , R ₁₃ and R ₁₆ 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.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The aryloxycarbonyl group represented by R ₁₂ , R ₁₃ and R ₁₆ R 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 is preferable.
Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The aryloxycarbonylamino group represented by R ₁₂ , R ₁₃ and R ₁₆ 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. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The imide group represented by R ₁₂ , R ₁₃ and R ₁₆ 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.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The heterocyclic thio group represented by R ₁₂ , R ₁₃ and R _{16 includes} a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. The heterocyclic thio group has 5 or 6 members.
It is preferable to have a membered heterocycle. Examples of the heterocyclic thio group include a 2-pyridylthio group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The sulfinyl group represented by R ₁₂ , R ₁₃ and R ₁₆ includes a sulfinyl group having a substituent and an unsubstituted sulfinyl group. Examples of the sulfinyl group include a phenylsulfinyl group.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The phosphoryl group represented by R ₁₂ , R ₁₃ and R ₁₆ 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.

Preferably, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ and
The acyl group represented by R ₁₂ , R ₁₃ and R ₁₆ includes an acyl group having a substituent and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 12 carbon atoms is preferable. Examples of the acyl group include an acetyl group and a benzoyl group.

Preferably, R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ ,
The sulfamoyl group represented by R ₁₁ , R ₁₄ and R ₁₅ is a sulfamoyl group having a substituent. Examples of the substituent include an aryl group. Examples of the sulfamoyl group include a phenylsulfamoyl group and a {(3-sulfo) phenyl} sulfamoyl group.

Preferably, R₂, R₃, R₆, R₇, R_Ten,
R₁₁, R₁₄And R₁₅The substituted sulfamoyl group represented by
As the group which may be further substituted with the substituent,
Group R ₁, R₂, R₃, R_Four, R_Five, R₆, R₇, R₈, R₉, R
_Ten, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅And R₁₆Illustrated in
A group can be mentioned.

M is a hydrogen atom, a metal element, a metal oxide,
Represents a metal hydroxide or metal halide. Preferred as M is, in addition to hydrogen atom, a metal element,
Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, M
n, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, A
u, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi
Etc. Preferred oxides include VO and GeO. Further, as the hydroxide, Si (OH) ₂ , Cr
(OH) ₂ , Sn (OH) _{2 and the} like are preferable. Further, as the halide, AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl,
FeCl, GaCl, ZrCl and the like can be mentioned. Especially, C
u, Ni, Zn, Al and the like are preferable, and Cu is most preferable.

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-, thio group -S-, a carbonyl group -CO-, a sulfonyl group -SO ₂ -, imino group -NH-, a methylene group -CH ₂
-, And groups formed by combining these are preferable.

Particularly preferable compounds as the phthalocyanine compound represented by the general formula (I) are the following (a) to (d).
A compound having a combination of (A) R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ , and R
With regard to ₁₆ , these are each independently a hydrogen atom or a halogen atom, a cyano group, particularly a hydrogen atom or a halogen atom, and among them, most preferably a hydrogen atom. (B) R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅
With regard to, it is preferable that these are each independently a hydrogen atom or a substituted sulfamoyl group, and in particular,
R ₂ and R ₃ , R ₆ and R ₇ , R ₁₀ and R ₁₁ , R ₁₄ and R ₁₅
In each of the above combinations, at least one of them is preferably a substituted sulfamoyl group, and among them, it is preferable that all the substituents of the sulfamoyl group have a substituent having 2 or more carbon atoms. (C) M is preferably Cu, Ni, Zn or Al, and most preferably Cu.

The phthalocyanine compound represented by the general formula (I) is preferably one having at least one lipophilic group having 2 or more carbon atoms in the molecule, and particularly a lipophilic group having 3 or more carbon atoms. Is preferred, and among them, the sum of lipophilic groups is most preferably a substituent having 8 or more carbon atoms.

The phthalocyanine compound represented by the general formula (I) has a solubility or dispersibility in a lipophilic medium when one molecule of the phthalocyanine compound has a substituent having a sum of carbon atoms of 8 or more. Especially good.

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), the phthalocyanine compound having the structure represented by the above general formula (II) is more preferable. The phthalocyanine compound represented by the general formula (II) of the present invention will be described in detail below.

[0094]

[Chemical 10]

In the general formula (II), X ₁ , X ₂ , X ₃ ,
And X ₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted It represents an aralkyl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted heterocyclic group. Of these, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group is preferable, and among them, a hydrogen atom is particularly preferable.

The alkyl group represented by X ₁ , X ₂ , X ₃ and X ₄ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group has 1 to 12 carbon atoms.
Alkyl groups of are preferred. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom. Examples of alkyl groups are methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3
-Sulfopropyl and 4-sulfobutyl are included.

The aryl group represented by X ₁ , X ₂ , X ₃ and X ₄ includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group has 6 carbon atoms.
The aryl group of -12 is preferable. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom and an alkylamino group. Examples of aryl groups include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The cycloalkyl group represented by X ₁ , X ₂ , X ₃ and X ₄ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. As the cycloalkyl group, a cycloalkyl group having 5 to 12 carbon atoms is preferable. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by X ₁ , X ₂ , X ₃ and X ₄ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group and the like. X ₁ ,
The aralkyl group represented by X ₂ , X ₃ and X ₄ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. The aralkyl group has 7 to 1 carbon atoms.
Two aralkyl groups are preferred. Examples of aralkyl groups include:
A benzyl group and a 2-phenethyl group are included.

The heterocyclic group represented by X ₁ , X ₂ , X ₃ and X 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 heterocyclic groups include 2-
A pyridyl group, a 2-thienyl group and a 2-furyl group are included.

Examples of the substituent when X ₁ , X ₂ , X ₃ and X ₄ can further have a substituent include R in the general formula (I).
₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ ,
It is the same as the examples of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , and the preferable examples of the substituent are also the same.

Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a substituted or unsubstituted aryl group.

L, m, n and p each independently represent an integer of 1 or 2, preferably 1.

Particularly preferred compounds as the phthalocyanine compound represented by the general formula (II) are the following (a) to (e)
A compound having a combination of (A) X ₁ , X ₂ , X ₃ , and X ₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and particularly preferably a hydrogen atom or a substituted group. Alternatively, it is an unsubstituted alkyl group, of which the hydrogen atom is particularly preferable. (B) Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a substituted aryl group, particularly preferably a sulfo group, a sulfonyl group, a sulfamoyl group and an acyl group, or a substituent of these groups. Is an aryl group substituted with a group having. (C) l, m, n, and p are preferably 1. (D) M is preferably Cu, Ni, Zn or Al, and most preferably Cu. (E) At _{least one} of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ and Y ₄ represents a substituent having 2 or more carbon atoms, and
The total number of carbon atoms of the substituents represented by X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ and Y ₄ is preferably 8 or more, and particularly,
At least one of Y ₁ , Y ₂ , Y ₃ and Y ₄ represents a substituent having 2 or more carbon atoms, and X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ and
The total number of carbon atoms of the substituents represented by Y ₂ , Y ₃ and Y ₄ is 8
It is preferable that at least one of Y ₁ , Y ₂ , Y ₃ and Y ₄ represents a substituent having 2 or more carbon atoms, and X ₁ , X ₂ , X ₃ and X ₄ , Y ₁ , Y ₂ , Y ₃ and Y ₄
Most preferably, the total number of carbon atoms of the substituents represented by is 10 or more.

Since the phthalocyanine compounds represented by the general formulas (I) and (II) have at least four or more substituted sulfamoyl groups in the molecule, they are soluble or dispersible in a lipophilic medium. Will be good.

Regarding the preferred combination of substituents of the compound represented by the general formula (II), a compound in which at least one of various substituents is a preferred group is preferable,
More preferred are compounds in which a greater number of different substituents are preferred groups, and most preferred are compounds in which all substituents are preferred groups.

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

[0108]

[Chemical 11]

In formula (III), W _{1 to} W ₂₀ are each independently a hydrogen atom, a halogen atom, an alkyl group,
Cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, Sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group,
Azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group,
It represents a sulfinyl group, a phosphoryl group or an acyl group, each of which may further have a substituent.

Among them, hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, alkylamino group, alkoxy group, amide group, arylamino group, sulfonamide group, carbamoyl group, Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, acyl group or an ionic hydrophilic group is preferable, more preferably a hydrogen atom, a halogen atom, a cyano group, an alkylamino group, a carbamoyl group, a sulfamoyl group and a sulfonyl group, particularly a hydrogen atom, A halogen atom, an alkylamino group, a sulfamoyl group and a sulfonyl group are preferable, and a hydrogen atom is most preferable.

However, W _{1 to} W ₅ , W _{6 to} W ₁₀ , W ₁₁ to
It is preferable that any one of W ₁₅ and W _{16 to} W ₂₀ is a substituted sulfamoyl group.

M, l, m, n and p have the same meanings as M, l, m, n and p in formula (II), and the preferred examples of M, l, m, n and p are also the same. is there.

Phthalocyanine represented by the general formula (III)
Particularly preferable combinations of the compounds are as follows.
It W₁~ W₂₀Are each independently a hydrogen atom, a halogen
Group atom, alkylamino group, acylamino group (-NHC
OR), a sulfonamide group (-NHSO₂-R), cal
Vamoyl group (-CONHR), sulfamoyl group, sulfone
Honyl group and ionic hydrophilic group are preferred, and particularly preferred
Is a hydrogen atom, an alkylamino group, an acylamino group (-N
HCOR), sulfonamide group (-NHSO₂-R),
Carbamoyl group (-CONHR), sulfamoyl group
Of these, the most preferable are hydrogen atom and carbamo.
An yl group and a sulfamoyl group. The parentheses above
R in represents a substituent. l, m, n and p are 4 ≦ l + m
+ N + p ≦ 8 is satisfied, and each independently 1 or 2
Yes, particularly preferably satisfying 4 ≦ l + m + n + p ≦ 6
However, the most preferable one among them is 1 (l = m =
n = p = 1). M is Cu, Ni, Z
n, Al, etc. are preferable, and Cu, Ni, Zn are particularly preferable.
Are preferred, and Cu is most preferred. General formula (III)
The phthalocyanine compound represented by₁~ W_Five, W₆~
W_Ten, W ₁₁~ W₁₅, And W₁₆~ W₂₀Less of each pair of
At least one of the pairs has 2 carbon atoms.
Represents the above substituents, and W₁~ W₂₀Replacement represented by
The total number of carbon atoms in the group is preferably 8 or more, and W₁
~ W_Five, W₆~ W_Ten, W₁₁~ W₁₅, And W₁₆~ W₂₀Is it
Each independently has a substituent having 2 or more carbon atoms, and
One, W₁~ W₂₀The total number of carbon atoms of the substituents represented by
The above is particularly preferable, and W₁~ W_Five, W₆~
W_Ten, W₁₁~ W₁₅, And W₁₆~ W₂₀Each independently,
Both have a substituent having 3 or more carbon atoms, and W₁~ W
₂₀The total number of carbon atoms of the substituents represented by is 12 or more.
And are most preferred.

The phthalocyanine compound represented by the general formula (III) has at least four substituted sulfamoyl groups in the molecule, and therefore has good solubility or dispersibility in a lipophilic medium.

Regarding the preferred combination of the substituents of the compound represented by formula (III), a compound in which at least one of the various substituents is a preferred group is preferable, and more various substituents are preferable groups. Are more preferred, and compounds in which all substituents are preferred groups are most preferred.

The phthalocyanine derivative represented by the above general formula (IV) of the present invention will be described in detail below. In addition,
The compound represented by the general formula (IV) is a novel compound having a specific structure which has not been known so far, and is useful as a water-soluble dye for inkjet and a synthetic intermediate for the water-soluble dye. It is a compound that can be used as an intermediate for pharmaceuticals and agricultural chemicals.

[0117]

[Chemical 12]

In the general formula (IV), W _{1 to} W ₂₀ , l,
m, n, p and M are W _{1 to} W ₂₀ in the general formula (III),
It has the same meaning as 1, m, n, p and M, and the preferred examples are also the same.

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

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

It is generally known to use various phthalocyanine derivatives in ink jet inks.
The phthalocyanine derivatives represented by the general formulas (I) to (IV) are inevitably substituted with a substituent Rn (n = 1
~ 16, R means merely a substituent, and is not specific to the R _{1 to} R ₁₆ substituents shown in the general formula (I)) (R _{1 to} R ₁₆ ) isomerism Although it may include the body, these substituted position isomers are often regarded as the same derivative without distinguishing from each other. In addition, even when the substituents of R include isomers, they are often regarded as the same phthalocyanine derivative without distinction. The case where the structures of the phthalocyanine compound defined in the present specification are different is described by the general formula (I). When the constituent atomic species of the substituent Rn (n = 1 to 16) are different, the number is different, and It is either when the positions are different.

In the present invention, the structures of the phthalocyanine compounds represented by the general formulas (I) to (IV) are different (in particular,
Substitution position) Derivatives are classified into the following three types and defined. (1) β-position substitution type: a phthalocyanine compound 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 (2) α- Position substitution type: (1 and / or 4 position, 5 and /
Or a phthalocyanine compound having a specific substituent at the 8-position, 9- and / or 12-position, 13- and / or 16-position) (3) α, β-position mixed substitution type: (Specify without regularity at 1- to 16-positions Phthalocyanine compound having a substituent of) In the present specification, the structure is different (particularly, the substitution position)
When explaining a derivative of a phthalocyanine compound, the above β
The notations of -position substitution type, α-position substitution type, and α, β-position mixed substitution type are used.

The phthalocyanine derivative used in the present invention is, for example, Shirai-Kobayashi Co., Ltd., published by IPC Co., Ltd., “Phthalocyanine-Chemistry and Function-” (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.

The phthalocyanine compound represented by the general formula (V) represented by the general formulas (II), (III) and (IV), which are the preferable phthalocyanine compounds of the present invention, is represented by the general formula (VI). Represented phthalonitrile compound and /
Alternatively, it is synthesized by reacting the diiminoisoindoline derivative represented by the general formula (VII) with the metal derivative represented by the general formula (VIII).

[0125]

[Chemical 13]

In the general formulas (VI) and (VII), R represents a substituted sulfamoyl group, and the substituent is represented by the general formulas (II) and (III).
And in the description of (IV), X ₁ , X ₂ , X ₃ , and X ₄ and Y ₁ ,
The substituents described above for Y ₂ , Y ₃ and Y ₄ . General formula (VIII): M- (Y) d In general formula (VIII), M is the same as M of said general formula (I)-(III), Y is a halogen atom, an anion anion, acetylacetonate. , A monovalent or divalent ligand such as oxygen, and d is an integer of 1 to 4. Examples of the metal derivative represented by the general formula (VIII) include Al, Si, Ti, V and M.
n, Fe, Co, Ni, Cu, Zn, Ge, Ru, R
h, Pd, In, Sn, Pt, Pb halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds,
Examples thereof include oxides and complexes. As a specific example, copper chloride,
Copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate,
Iron chloride, zinc chloride, zinc bromide, zinc iodide, zinc acetate, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese chloride, lead chloride, acetic acid Examples thereof include lead, indium chloride, titanium chloride, tin chloride and the like.

The metal derivative and the phthalonitrile compound represented by the general formula (VI) are used in a molar ratio of 1: 3 to 1: 6.
Is preferred. The amount of the metal derivative and the diiminoisoindoline derivative represented by the general formula (VII) 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-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol,
Benzyl alcohol, ethylene glycol, propylene glycol, ethoxy ethanol, propoxy ethanol, butoxy ethanol, dimethyl amino ethanol,
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 1 with respect to 1 mol of the phthalonitrile compound.
It is 0 times mol, preferably 0.5 to 2 times mol. The reaction temperature is 80 to 300 ° C., preferably 100 to 250 ° C., preferably 130 to 230 ° C.
It is particularly preferable to carry out the reaction within the range of the reaction temperature. 80 ° C
In the following, the reaction speed is extremely slow. If the temperature is higher than 300 ° C, the phthalocyanine compound may be decomposed. The reaction time is 2 to 20 hours, preferably 5 to 15 hours, particularly preferably 5 to 10 hours. A large amount of unreacted raw material exists in 2 hours or less, and decomposition of the phthalocyanine compound may occur in 20 hours or more.

The products obtained by these reactions are:
After treatment according to the usual post-treatment method of organic synthesis reaction,
It can be provided with or without purification. That is, for example, without purifying the product liberated from the reaction system,
Alternatively, recrystallization, column chromatography (for example,
Gel permeation chromatography (SEPHADE
XTMLH-20: manufactured by Pharmacia) and the like, and can be provided by performing an operation of purifying alone or in combination.

Alternatively, after completion of the reaction, the reaction solvent may be distilled off, or it may be poured into water or ice without distillation and neutralized or liberated without neutralization may be purified or repurified. It can be provided after performing an operation of purifying by crystallization, column chromatography or the like, alone or in combination. Alternatively, after completion of the reaction, the reaction solvent may be distilled off, or it may be poured into water or ice without distillation to neutralize it, or purified by extraction with an organic solvent / aqueous solution without neutralization. It can be provided without any treatment or after performing an operation of purifying by crystallization or column chromatography alone or in combination.

It is represented by the general formula (V) thus obtained.
The phthalocyanine compound is usually R ¹~ R^FourEach replacement position of
The following general formulas (a) -1 to (a)-which are isomers of
It is a mixture of the compounds represented by 4.

[0133]

[Chemical 14]

[0134]

[Chemical 15]

[0135]

[Chemical 16]

[0136]

[Chemical 17]

That is, general formulas (a) -1 to (a) -4
The compound represented by is a β-position substitution type (2 and / or 3
1st, 6th and / or 7th, 10th and / or 11th, 1st
A phthalocyanine compound having a specific substituent at the 4- and / or 15-position), which is a compound having a completely different structure (substitution position) from the α-position substitution type and the α, β-position mixed substitution type. This is an extremely important structural feature as a means for solving the above. The effect of improving the hue, light fastness, ozone gas resistance and the like brought about by the structural characteristics of the β-position substitution type cannot be predicted at all from the prior art.

In the present specification, the term "resistance to ozone gas" is used to represent the resistance to ozone gas, and also includes the resistance to oxidizing atmospheres other than ozone gas. That is, the above-mentioned phthalocyanine compound represented by the general formula (I) according to the present invention is a nitrogen oxide contained in exhaust gas of automobiles, a sulfur oxide contained in exhaust gas of thermal power plants and factories, and these are photochemically exposed to sunlight. Oxidation present in general environment such as ozone gas generated by radical chain reaction of oxygen, photochemical smog rich in oxygen-nitrogen and oxygen-hydrogen radicals, hydrogen peroxide radicals generated from places where special chemicals such as beauty salons are used. It is characterized by strong resistance to natural gas. Therefore, when oxidative deterioration of an image such as outdoor advertisement or guidance in a railroad facility restricts the image life, by using the phthalocyanine compound according to the present invention as an image forming material, resistance to an oxidizing atmosphere, that is, So-called ozone gas resistance can be improved.

Specific examples of the phthalocyanine compound represented by the general formula (I) (exemplified compounds 101 to 150) are shown in Table 1 below.
~ As shown in Table 10, the phthalocyanine compound used in the present invention is not limited to the following examples.

[0140]

[Table 1]

[0141]

[Table 2]

[0142]

[Table 3]

[0143]

[Table 4]

[0144]

[Table 5]

[0145]

[Table 6]

[0146]

[Table 7]

[0147]

[Table 8]

[0148]

[Table 9]

[0149]

[Table 10]

[Synthesis Example] The synthesis method of the phthalocyanine compound derivative of the present invention is described in detail below with reference to the synthesis example, but the starting material, the dye intermediate and the synthesis route are not limited thereto. In the following,
λmax means the absorption maximum wavelength, and εmax means the molar absorption coefficient at the absorption maximum wavelength.

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

[0152]

[Chemical 18]

Synthesis Example 1: Synthesis of Compound A 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-sodium 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 produced solid matter 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 1M hydrochloric acid saturated saline solution. 700 mL of the obtained solid
Was dissolved in 0.1 M aqueous sodium hydroxide 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 to salt 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
After washing with 00 mL and drying, 29.25 g of Compound A was obtained as blue crystals. λmax: 629.9 nm; εmax =
6.11 x 10 ⁴ (in aqueous solution). The obtained Compound A was analyzed (mass spectrometry: measured by various instrumental analysis methods such as ESI-MS, elemental analysis, neutralization titration), and as a result, phthalocyanine copper (II) defined in the present specification, that is, substitution The position is β-position substitution type [(2 or 3 of each benzene nucleus
Rank), (6 or 7 rank), (10 or 11 rank), (1
4 or 15-position) each has one sulfo group, and copper phthalocyanine has a total of four sulfo groups in the molecule].

Synthesis Example 2: Synthesis of Compound B Chlorosulfonic acid 1 was placed in a three-necked flask equipped with a cooling tube.
50 mL was added, and 19.0 g of the compound A synthesized above was slowly added in portions while stirring at 30 ° C. or lower. After stirring for 30 minutes at 20 ℃, 60g at 25 ℃ or below
Phosphorus pentachloride was slowly added in portions. 140 reaction mixture
The mixture was heated to ℃ and stirred at the same temperature for 3 hours. After cooling to 80 ° C., 30 mL of thionyl chloride was added dropwise over 15 minutes. Subsequently, the reaction solution was heated to 80 ° C. and stirred at the same temperature for 2 hours. After cooling to 10 ° C., the reaction mixture was diluted to 1
The mixture was gradually added to a mixture of 000 mL of water and 500 g of ice to precipitate a blue crystal target substance. The temperature in the suspension was kept at 0-5 ° C by supplementary addition of ice. After further stirring at room temperature for 1 hour, the mixture was filtered through a Nutsche filter and washed with 1500 mL of cold water. Subsequently, the crystals were washed with 150 mL of cold acetonitrile, and then dried under reduced pressure in a desiccator containing a desiccant overnight to give compound B (M.
W. 970.09) 15.6 g was obtained as blue crystals.
As a result of analyzing the obtained compound B, it was confirmed that it was phthalocyanine copper (II) defined in the present specification, that is, tetrasulfonyl chloride having a substitution position of β-type.
Further, 0.01 part of the obtained crystals was quenched with 2-ethylhexyloxypropylamine / acetone, and then HPL
Purity test at C (detection wavelength 254 nm; 0.1% acetic acid /
Triethylamine buffer system; THF / H ₂ O = 7
/ 3), relative area% = 90.95% [Cu-
Was _{Pc (-SO 2 NH-R)} 4 test as the sum of the derivatives].

Synthesis Example 3: Synthesis of Specific Compound Example 101 6.2 g of 4-octylaniline was dissolved in 50 mL of DMAc, and 3.0 g of the compound B synthesized above was added while stirring at an internal temperature of 5 ° C. The reaction was gradually added. After stirring at room temperature for 30 minutes, the mixture was heated to 55 ° C. and stirred at the same temperature for 1 hour. After cooling to 20 ° C., the reaction solution was poured into 300 mL of water and then stirred at room temperature for 30 minutes, and the precipitated crude crystals were filtered with a Nutsche, washed with 100 mL of cold water, and dried. The obtained crude crystals were subjected to silica gel column chromatography (CH ₂ Cl ₂ / THF) to produce a by-product [eg Cu-Pc- (SO ₃ X) _m (SO ₂ NHA
r) _n derivative: m + n = 4, m ≠ 0] was removed to obtain 4.1 g of Exemplified Compound 101. λmax = 628.5 nm;
εmax = 1.84 × 10 ⁵ (in DMF).

Synthesis Example 4: Synthesis of Specific Compound Example 101 by Alternative Method Using the following compound (F) as a starting material under the reaction conditions described in detail, β-position substitution type: Cu-Pc- {SO ₂ NH-
A (4-octylphenyl)} ₄ derivative was synthesized. As a result of analyzing the obtained compound, the mixture distribution of substitution positions [(2 or 3 position) of each benzene nucleus, (6 or 7
Position), (10 or 11 position), (14 or 15 position) has one 4-octylphenyl group],
It was a β-position-substituted derivative defined in the present specification, which had a total of four substituted sulfemoiol groups in one molecule of copper phthalocyanine, and was the same compound as that synthesized in Synthesis Example 3. (Though the synthesis routes are different, it is clear from the common sense of organic synthesis that the compounds synthesized in Synthesis Example 3 and Synthesis Example 4 are the same β-position substituted phthalocyanine copper (II).)

[0157]

[Chemical 19]

[Synthesis Example of Comparative Compound] Comparative Synthesis Example 1 (a) Synthesis of Comparative Compound 1 Chlorosulfonic acid 15 was added to a three-necked fusco equipped with a cooling pipe.
0 mL was added, and 25.0 g of copper phthalocyanine was slowly added in portions while stirring and keeping a temperature not exceeding 20 ° C. This mixture was then heated to 100 ° C. for 1 hour and further heated to 135 ° C. for 1 hour, and kept at the same temperature for 4 hours until gas generation was completed. Stir for hours. Then, this reaction liquid was cooled to 75 ° C., and then 30 mL of thionyl chloride was added dropwise over 30 minutes. Subsequently, the reaction solution was heated to 80 ° C. and stirred at the same temperature for 2 hours. Cooled to 10 ° C. Then, the reaction solution was mixed with 1500 mL of water and 50
It was slowly added to a mixture with 0 g of ice to precipitate a target substance of blue crystals. The temperature in the suspension was kept at 0-5 ° C by supplementary addition of ice. After further stirring at room temperature for 1 hour, the mixture was filtered through a Nutsche filter and washed with 2500 mL of cold water. Subsequently, the crystals were washed with 100 mL of cold acetonitrile and then dried under a reduced pressure in a desiccator containing a desiccant overnight to obtain 35.5 g of Comparative Compound 1 shown below as blue crystals. As a result of analyzing the obtained compound, the substitution position of phthalocyanine copper (II) defined in the present specification is α, β-mixed type, and the number of substitution is sulfonyl chloride of di-, tri-, tetra-mixture. It was confirmed that there is. The obtained crystal (0.01 part) was quenched with 2-ethylhexyloxypropylamine / acetone, and then subjected to a purity test by HPLC (detection wavelength 254 nm;
1% acetic acid / triethylamine buffer system; THF /
H ₂ O = 7/3), relative area% = 80.52
% [Cu-Pc sum of (-SO ₂ NH-R) n Derivative
Met.

[0159]

[Chemical 20]

(B) Synthesis of Comparative Compound 2 JP-A-10-130517, WO 00/08101
Comparative Compound 2 was synthesized using the method described in No. WO 00/08103, etc., and the obtained compound was analyzed. As a result, compared with Comparative Compound 1, the mixture distribution of substitution positions was slightly smaller. Purity as sulfonyl chlorides having different mixing distributions of substitution numbers (2 substitutions, 3 substitutions, 4 substitutions) [Cu-Pc described above]
Although the difference between the test] as the sum of (-SO ₂ NH-R) n derivative thereof, any method described comparative compound 1 and comparative compound 2 synthesized in (Comparative Compound synthesis method 1), herein It was confirmed that the phthalocyanine copper (II) -substitution position defined in (4) was α, β-mixed type and the number of substitution was di-, tri-, tetra-mixed sulfonyl chloride.

(C) Synthesis of Comparative Compound 3 Starting from the following compound (G) synthesized by the method described in JP-A-10-204053, etc., under the reaction conditions described in detail in the publication. , Α − shown below
A position-substituted phthalocyanine copper (II) derivative was synthesized. As a result of analyzing the obtained compound, the phthalocyanine copper (II) -substitution position defined in this specification was found to be α-position substitution type [(1 or 4 position) of each benzene nucleus, (5 or 8 position). ), (9 or 12-position), (13 or 16-position) has one sulfo group and a total of four sulfo groups in one molecule of copper phthalocyanine].

[0162]

[Chemical 21]

[0163]

[Chemical formula 22]

(D) Synthesis of Comparative Compound 4 Using Comparative Compound 2 as a starting material, the same operation as in Synthesis Example 3 was carried out to give Comparative Compound 4 (Comparative Compound with Derivative of Specific Compound Example 101). ) Got.

[0165]

[Chemical formula 23]

The use of the compound of the present invention as a dye includes an image recording material for forming an image, particularly a color image. Specifically, it is an inkjet recording material, a heat-sensitive transfer image recording material, and a photosensitive material. Pressure recording material, electrophotographic recording material, transfer type silver halide photosensitive material,
Printing inks, recording pens, etc., preferably inkjet recording materials, heat-sensitive transfer type image recording materials, recording materials using electrophotography, and more preferably inkjet recording materials. US Pat. No. 4,808,5
No. 01, JP-A-6-35182, etc., it can also be applied to color filters used in solid-state imaging devices such as LCDs and CCDs, and dyeing of various fibers. The compound of the present invention is used by adjusting physical properties such as solubility and heat transfer property suitable for its use by a substituent. Further, 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.

[Ink and Inkjet Ink] The ink of the present invention (including inkjet ink) will be described below. The ink can be prepared by dissolving and / or dispersing the phthalocyanine compound in a lipophilic medium or an aqueous medium. Preferably, an aqueous medium is used. Other additives as needed,
It is 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, ultraviolet absorbers, preservatives, mildew-proofing agents, pH adjusting agents, surface tension adjusting agents,
Known additives such as defoaming 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 directly added 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 caused by the ink, especially the ink jet ink, drying at the ink jet port of the ink jet recording nozzle.

As the anti-drying agent, an 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-
Examples thereof include imidazolidinone, heterocycles such as N-ethylmorpholine, sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, and 3-sulfolene, polyfunctional compounds such as diacetone alcohol and diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. The above-mentioned anti-drying agents may be used alone or in combination of two or more kinds. It is preferable that the drying inhibitor is contained in the ink in an amount of 10 to 50% by mass.

The penetration enhancer is preferably used for the purpose of allowing the ink, particularly the inkjet 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. . When these are contained in the ink in an amount of 5 to 30% by mass, a sufficient effect is usually obtained, and it is preferable to use them in an addition amount range that does not cause bleeding of printing and paper drop (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.
0492, 56-21141, JP-A-1
Cinnamic acid compounds described in JP-A-0-88106,
JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, and JP-A-10-182621.
Compounds disclosed in Japanese Patent Publication No. 8-501291 and Research Disclosure N
o. Compounds and stilbene compounds described in No. 24239,
A compound typified by a benzoxazole-based compound that emits fluorescence by absorbing ultraviolet light, that is, a so-called fluorescent whitening agent can also be used.

The anti-fading agent is used for the purpose of improving the storability of 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. 176
No. 43, Item VII, I to J, ibid. 15162, the same No. 18716, page 650, left column, same No. 36544
Pp. 527, ibid. 307105, page 872, same N
o. The compounds described in the patent cited in 15162 and the compounds included in the general formulas and the compound examples of the representative compounds described on pages 127 to 137 of JP-A No. 62-215272 can be used.

As a fungicide, sodium dehydroacetate,
Sodium benzoate, sodium pyridinethione-1-
Oxide, p-hydroxybenzoic acid ethyl ester,
1,2-benzisothiazolin-3-one and salts thereof and the like can be mentioned. These are 0.02-1.0 in the ink
It is preferable to use 0% by mass.

As the pH adjusting agent, a neutralizing agent (organic base, inorganic alkali) can be used. The pH adjuster is for the purpose of improving the storage stability of the inkjet ink,
The inkjet ink is preferably added at pH 6 to 10 for summer, and more preferably at 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.
mPa · s is preferable. Furthermore, 25-60 mN / m is preferable. The viscosity of the inkjet ink of the present invention is preferably 30 mPa · s or less. It is more preferable to adjust to 20 mPa · s or less. 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 (198
Those listed as the surfactants described in (9 years) can also be used.

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. 2000-78.
No. 491, No. 2000-80259, No. 2000-62370, dispersed in the aqueous medium colored fine particles containing a dye and an oil-soluble polymer, Japanese Patent Application No. 2000-78454, No. 2000-78491, 20
It is preferable to disperse the dye of the present invention dissolved in a high boiling point organic solvent in an aqueous medium as described in Nos. 00-203856 and 2000-203857. The specific method for dispersing the dye 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 azo dye may be dispersed in a fine particle state as it is as a solid. 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 ink, in addition to the above-mentioned patent publications, etc.
No. 436, No. 5-295312, No. 7-97541.
No. 7-82515, No. 7-118584, No. 11-286637, Japanese Patent Application No. 2000-87539, and the like, and can be used for preparing the ink of the present invention.

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 water-miscible organic solvents are alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols. Classes (for example, 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, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether ,
Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (eg,
Ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (for example,
Formamide, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone) included. Two or more water-miscible organic solvents may be used in combination.

The ink of the present invention preferably contains 0.2 to 10 parts by mass of the phthalocyanine compound per 100 parts by mass of the ink. Further, in the ink of the present invention, other colorants may be used together with the phthalocyanine compound. When two or more colorants are used in combination, the total content of the colorants containing the compound of the present invention is preferably within the above range.

The inkjet ink of the present invention can be used not only for monochromatic image formation but also for full 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., condensed polycycles such as dioxazine dyes, etc. Examples thereof include 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 dye may exhibit yellow, magenta, and cyan colors only when a part of the chromophore is dissociated, and the counter cation in this case is an alkali metal or an inorganic cation such as ammonium. It may be an organic cation such as a pyridinium or 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 ink to obtain a known image receiving material, that is, plain paper or resin-coated paper, for example, JP-A-8-169172 and JP-A-8-169172.
-27693, 2-272670, 7
-276789, 9-323475, JP-A-62-238783, and JP-A-10-1539.
No. 89, No. 10-217473, No. 10-2.
No. 35995, No. 10-337947, No. 1
Inkjet-dedicated papers and films described in JP-A Nos. 0-217597 and 10-337947,
An image is formed on electrophotographic paper, cloth, glass, metal, ceramics, and the like.

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 Applications 2000-363090, 2000-315231, and
2000-354380, 2000-343944, 2000-268952,
The methods described in 2000-299465 and 2000-297365 can be preferably used.

The recording paper and recording film used for ink jet printing using the ink of the present invention will be described below. Supports for recording paper and recording film are chemical pulp such as LBKP and NBKP, G
P, PGW, RMP, TMP, CTMP, CMP, CG
It consists of mechanical pulp such as P, waste paper pulp such as DIP,
If necessary, conventionally known pigments, binders, sizing agents,
Mixing additives such as fixing agent, cationic agent, paper strengthening agent,
Those manufactured by various devices such as a Fourdrinier paper machine and a cylinder paper machine can be used. In addition to these supports, synthetic paper or plastic film sheet may be used. The thickness of the support is 10 to 250 μm, and the basis weight is 10 to 250 g.
/ M ² is desirable. The support may be provided with the ink receiving layer and the back coat layer as it is, or may be provided with the ink receiving layer and the back coat layer after the size press or the anchor coat layer is provided with starch, polyvinyl alcohol or the like. 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, as the support,
A paper and a plastic film having both surfaces laminated with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and their copolymers) are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support includes
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, both silicic acid anhydride obtained by the dry production method and hydrous silicic acid obtained by the wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

The aqueous binder contained in the ink receiving layer includes polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, 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 may contain a mordant, a water-proofing agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For 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. 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 benzophenone or benzotriazole ultraviolet absorbers. Of these, zinc sulfate is particularly preferable.

The surfactant is a coating aid, a peelability improver,
Functions as a slipperiness improver or antistatic agent.
Regarding the surfactant, JP-A-62-173463,
There is a description in each publication of the same 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.

The aqueous binder contained in the back coat layer includes styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin. , 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 cracking prevention. Regarding the polymer latex, JP-A Nos. 62-245258 and 62-1
It is described in each publication of 316648 and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to 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 in which ink is ejected by using electrostatic attraction, a drop-on-demand system in which vibration pressure of a piezo element is used. (Pressure pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate the ink and the ink is ejected by using radiation pressure, and a bubble is formed by heating the ink and the generated pressure is used It is used in thermal inkjet systems. 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.

[Color Toner] As the binder resin for the color toner into which the phthalocyanine compound of the present invention is introduced, all commonly used binders can be used. For example, styrene resin, acrylic resin, styrene / acrylic resin, polyester resin, etc. may be mentioned. Inorganic fine powder or organic fine particles may be externally added to the toner for the purpose of improving fluidity and controlling charging. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. In addition, it is preferable that these have a number average primary particle diameter of 10 to 500 nm,
Further, it is preferable to add 0.1 to 20% by mass to the toner.

As the release agent, all the release agents which have been conventionally used can be used. Specific examples thereof include olefins such as low molecular weight polypropylene / low molecular weight polyethylene / ethylene-propylene copolymer, and microcrystalline wax / carnauba wax / sazol wax / paraffin wax. The addition amount of these is preferably 1 to 5% by mass in the toner.

The charge control agent may be added if necessary, but a colorless one is preferable from the viewpoint of color developability. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron or ferrite, or a resin coated carrier in which the surface of the magnetic material particles is coated with a resin may be used. The volume average particle diameter of the carrier is preferably 30 to 150 μm.

The image forming method to which the toner of the present invention is applied is not particularly limited. For example, a method of repeatedly forming a color image on a photoconductor and then transferring the color image, or a photoconductor. Examples of the method include sequentially transferring the images formed on the intermediate transfer member or the like, forming a color image on the intermediate transfer member or the like, and then transferring the image to an image forming member such as paper to form a color image.

[Heat-sensitive transfer material] The heat-sensitive recording material moves in accordance with the ink sheet in which the phthalocyanine compound of the present invention is coated on the support together with the binder, and the heat energy applied from the thermal head according to the image recording signal. It is composed of an image-receiving sheet that fixes the dye. The ink sheet is prepared by dissolving the compound of the present invention in a solvent together with a binder, or by dispersing the compound in a solvent in the form of fine particles to prepare an ink liquid, coating the ink on a support and appropriately drying. Can be formed. As the preferable binder resin, ink solvent, support and image-receiving sheet which can be used, those described in JP-A-7-137466 can be preferably used.

In order to apply the heat-sensitive recording material to a heat-sensitive recording material capable of recording a full-color image, a cyan ink sheet or a magenta image containing a heat-diffusible cyan dye capable of forming a cyan image can be formed. It is preferable that a magenta ink sheet containing a heat-diffusible magenta dye and a yellow ink sheet containing a heat-diffusible yellow dye capable of forming a yellow image are successively applied on a support to form a yellow image. In addition, an ink sheet containing a black image forming substance may be further formed, if necessary.

[Color Filter] As a method for forming a color filter, a method of first forming a pattern with a photoresist and then dyeing it, or JP-A-4-1635
52, JP-A-4-128703, and JP-A-4-175753, there is a method of forming a pattern with a photoresist containing a dye. As a method used when introducing the phthalocyanine compound of the present invention into a color filter, any of these methods may be used, but preferred methods are disclosed in JP-A-4-175753 and JP-A-6-35182. As described, a positive resist composition containing a thermosetting resin, a quinonediazide compound, a cross-linking agent, a dye and a solvent, and after coating it on a substrate, it is exposed through a mask to expose the exposed portion. An example of a method for forming a color filter includes developing to form a positive resist pattern, exposing the positive resist pattern over the entire surface, and then curing the exposed positive resist pattern. In addition, a black matrix is formed according to a conventional method, and RGB primary color system or Y,
MC complementary color filter can be obtained.

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

[0207]

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

[Example 1] Deionized water was added to the following ingredients to make 1 liter, and then 1 while heating at 30-40 ° C.
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 a cyan ink liquid.

(Preparation of Ink Liquid A) 20.0 g of phthalocyanine compound (Specific Compound Example 101; oil-soluble dye),
Benzotriazole 0.06g and PROXEL XL
2, 1.8 g were dissolved in 230 g of diethylene glycol monobutyl ether, 80 g of 2-pyrrolidone, 17.9 g of triethanolamine and 50 ml of ethyl acetate at 70 ° C. To this solution, 500 ml of deionized water was added while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse-grained dispersion is
Microfluidizer (MICROFLUIDEX
The particles were made into fine particles by passing it 5 times at a pressure of 600 bar in INC). The resulting emulsion was desolvated with a rotary evaporator until the odor of ethyl acetate disappeared. 20 g of diethylene glycol and 1 of glycerin were added to a fine emulsion of the hydrophobic dye thus obtained.
20 g, SURFYNOL465 (AirProduc
ts & Chemicals) 8.5 g, deionized water 9
An ink was prepared by adding 00 ml.

(Preparation of ink liquids B to G) Ink liquid A except that the phthalocyanine compound (specific compound example 101; oil-soluble dye) of ink liquid A was changed to the phthalocyanine compound (oil-soluble dye) shown in Table 11 below. Ink liquid B as in
~ G were produced. At this time, as an ink liquid for comparison,
Ink liquids 101 and 102 were prepared using the following compounds. When the dye was changed, it was used so that the addition amount was equimolar to the ink liquid A. When two or more dyes were used in combination, they were used in equimolar amounts.

(Image recording and evaluation) The above examples (ink liquids A to G) and comparative examples (ink liquids 201 to 204)
The following evaluations were performed for the inkjet ink. The results are shown in Table-11. In Table-11, "color tone", "paper dependency", "water resistance" and "light resistance" refer to each ink jet ink jet printer (manufactured by EPSON Corporation; PM-700C).
With photo glossy paper (PMSON paper manufactured by EPSON <Glossy> (K
(A420PSK, EPSON) and then evaluated.

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

Preferred a *: -35.9 or more and 0 or less, Preferred b *: -50.4 or more and 0 or less ◯: Both a * and b * are preferable regions Δ: Area where only one of a * and b * is preferable X: Both a * and b * are outside the preferred range

<Paper Dependency> The color tone of the image formed on the photo glossy paper and the image formed separately on the plain paper for PPC are compared, and when the difference between the images is small, A (good), both When the difference between the images was large, it was evaluated as B (defective) in two stages.

<Water resistance> The photo glossy paper on which the image was formed 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 7 days using a weather meter (Atlas CI65), and the image density before and after the xenon irradiation was measured by a reflection densitometer. (X-Rite31
0TR) and evaluated as the residual rate of the dye.
The reflection density was measured at three points of 1, 1.5 and 2.0. At any concentration, the dye residual rate is 70% or more, A, 1 or 2 points is less than 70% B, and 7 at all concentrations.
The case of less than 0% was set as C and evaluated in three stages.

<Dark heat storability> The photo glossy paper on which the image was formed was stored as a sample for 7 days under the conditions 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 7 days in a box set at 5 ± 0.1 ppm, room temperature, and a dark place.
Reflection densitometer (X-Rit
e310TR) and evaluated as the residual dye rate. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box is AP
PLICS ozone gas monitor (model: OZG-E
M-01). 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.

[0219]

[Table 11]

As is apparent from Table-11, the ink-jet ink of the present invention was excellent in color tone, less dependent on paper, and excellent in water resistance, light resistance and ozone gas resistance. In particular, it is clear that the image storability such as light resistance and ozone gas resistance is excellent.

[Example 2] The same cartridge prepared in Example 1 was used to print an image on the inkjet paper photo glossy paper EX manufactured by Fuji Photo Film Co., Ltd. using the same machine as in Example 1, and the same evaluation as in Example 1 was performed. Example 1
Similar results 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 For each of the phthalocyanine compounds of the present invention (compounds 101, 121, 141 and 161), 3 parts by weight of the compound, a resin for toner [styrene-acrylic acid ester copolymer; trade name Heimer TB -1000F (manufactured by Sanyo Kasei)] 100 parts by mass are mixed and pulverized in a ball mill, heated to 150 ° C. for melt-mixing, cooled, coarsely pulverized using a hammer mill, and then finely pulverized by an air jet type fine pulverizer. Crushed. Further classification was carried out to select 1 to 20 micro to prepare a toner. To 10 parts of this toner, carrier iron powder (trade name EFV25
0/400; made by Nippon Iron Powder) 900 parts were uniformly mixed to obtain a developer. Similarly, a sample was prepared in the same manner except that the comparative colorant shown in Table 12 was used in an amount of 3 parts by mass for the dye and 6 parts by mass for the pigment. Using these developers, copying was performed with a dry plain paper electrophotographic copying machine [trade name: NP-5000; manufactured by Canon Inc.].

In the evaluation test, a reflection image (image on paper) and a transmission image (OHP image) were prepared on paper and OHP by the above-mentioned image forming method using a developer using a color toner containing the compound of the present invention. Then, it carried out by the method shown below. The toner adhesion amount is 0.7 ± 0.
The evaluation was made in the range of 05 (mg / cm ² ).

The hue and light fastness of the obtained image were evaluated. The hue was visually evaluated on the basis of 3 grades: best, good and bad. The evaluation results are shown in Table 12. Table 1
Out of 2, ◯ indicates the best hue; △ indicates good.
X indicates that the hue was poor. Regarding the light fastness, after measuring the image density Ci immediately after recording, the image was irradiated with xenon light (85,000 lux) for 5 days using a weather meter (Atlas C.165), and then the image was re-recorded. The density Cf was measured, and the dye residual ratio ({(Ci-Cf) / Ci} × 10
0%) was calculated and evaluated. Image density is measured by a reflection densitometer (X
-Rite310TR). The evaluation results are shown in Table 12. In Table 12, the case where the residual dye ratio is 90% or more is indicated by ◯, the case of 90 to 80% is indicated by Δ, and the case of less than 80% is indicated by x.

The transparency of the OHP image was evaluated by the following method. "330 type self-recording spectrophotometer" made by Hitachi Ltd.
The visible spectral transmittance of the image is measured with an OHP sheet on which no toner is carried as a reference by
The spectral transmittance in nm was obtained and used as a measure of the transparency of the OHP image. A spectral transmittance of 80% or more was evaluated as ◯, 70 to 80% was evaluated as Δ, and 70% or less was evaluated as x. The above results are shown in Table 12.

[0227]

[Table 12]

[0228]

[Chemical formula 24]

[0229]

[Chemical 25]

As is clear from Table 12, the phthalocyanine compound of the present invention is superior in light fastness to the comparative dye, has a bright hue, has high transparency, and uses the color toner of the present invention. By doing so, faithful color reproduction and high OH
Having the P quality, the color toner of the present invention is suitable for use as a full color toner. Further, since it has good light resistance, it is possible to provide an image that can be stored for a long period of time.

[Example 5] <Method for producing color filter> In this example, the results of applying a phthalocyanine compound to a color filter are shown. The color filter was produced by the following method. That is, a silicon wafer is spin-coated with a positive resist composition containing a thermosetting resin, a quinonediazide compound, a cross-linking agent, a dye and a solvent, and the solvent is evaporated by heating, followed by exposure through a mask to decompose the quinonediazide compound. Let If necessary, after heating, development was carried out to obtain a mosaic pattern. The exposure was performed by an i-line exposure stepper HITACHI LD-5010-i (NA = 0.40) manufactured by Hitachi Ltd.
As the developing solution, SOPD or SOPD-B manufactured by Sumitomo Chemical Co., Ltd. was used. <Preparation of positive resist composition> m-cresol / p-
Cresol / formaldehyde (reaction molar ratio = 5/5 /
7.5) 3.4 parts by mass of cresol novolak resin (polystyrene-equivalent mass average molecular weight 4300) obtained from the mixture,
The following formula

[0232]

[Chemical formula 26]

O-naphthoquinonediazide-5-sulfonic acid ester prepared by using the phenol compound represented by the formula (on average, two hydroxyl groups are esterified) 1.8
By mass, 0.8 parts by mass of hexamethoxymethylolated melamine, 20 parts by mass of ethyl lactate and 1 part by mass of the phthalocyanine compound of the present invention shown in Table 13 were mixed to obtain a positive resist composition. <Preparation of Color Filter> A silicon wafer was spin-coated with the obtained positive resist composition, and then the solvent was evaporated. After exposing the silicon wafer, heat it at 100 ° C and remove the exposed area by alkali development to remove 0.8 μm.
A positive colored pattern having a resolution of m was obtained. After exposing the whole surface, it was heated at 150 ° C. for 15 minutes to obtain a complementary color filter of cyan.

<Comparative Example> A positive resist composition was obtained by mixing 1 part by mass of Comparative Dye 7 below in place of the cyan phthalocyanine compound of the present invention used in the above Examples.
A silicon wafer was spin-coated with this positive resist composition, and then the solvent was evaporated. After exposing the silicon wafer, it was alkali-developed to obtain a positive type colored pattern having a resolution of 1 μm. After exposing the whole surface, 150 ℃ ・ 10
After heating for a minute, a magenta color filter was obtained.

<Evaluation> The transmission spectrum of the obtained cyan color filter was measured, and the short-wave side and long-wave side breaks of the spectrum important for color reproduction were relatively evaluated. ○ is good, △
Represents an acceptable level, and x represents an unacceptable level. In addition, a weather meter (Atlas C.I65)
Xenon light (85000 lx) was irradiated for 7 days, and the image density before and after irradiation with xenon was measured to evaluate the residual dye rate.

[0236]

[Table 13]

[0237]

[Chemical 27]

Compared with the comparative example, the phthalocyanine compound of the present invention has sharp cuts on the short wave side and the long wave side of the spectrum,
It had excellent color reproducibility. It was also shown that the light fastness is superior to that of the comparative compound.

Example 6 The test of Example 6 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, H.Iwano, et al; Journal of Imaging Science a as a test method for oxidizing gas resistance simulating an outdoor environment that is exposed to oxidizing gas such as automobile exhaust gas and sunlight.
ND Technology, 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 results were the same as in Example 1.

[0240]

EFFECTS OF THE INVENTION According to the present invention, 1) As a dye of three primary colors, it has excellent absorption characteristics with excellent color reproducibility, and has sufficient fastness to light, heat, humidity and active gas in the environment. Providing a novel phthalocyanine compound, 2) It has excellent hue and fastness used for inks such as ink jet and other printing inks, thermal recording ink sheets, electrophotographic color toners, color filters for various displays and imaging devices. 3) Inkjet, which provides a coloring composition, and 3) In particular, which has a good hue by using the phthalocyanine compound and can form an image having high fastness to an active gas in light and environment, particularly ozone gas. An ink and an inkjet recording method can be provided, and 4) a method for improving ozone gas fading resistance of an inkjet recorded image can be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 11/00 G02B 5/22 2H111 G02B 5/20 101 G03F 7/004 505 4J037 5/22 B41M 5/26 K 4J039 G03F 7/004 505 B41J 3/04 101Y G03G 9/09 G03G 9/08 361 (72) Inventor Kaji Yabuki 210 Nakanishuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film Co., Ltd. (72) Inventor Omatsu Sada Kanagawa Prefecture 210 Nakanuma, Minamiashigara-shi Fuji Photo Film Co., Ltd. F-term (reference) 2C056 EA13 FC02 2H005 AA06 AA21 CA21 CA22 2H025 AA11 CC11 2H048 BA57 BA64 CA04 CA09 CA14 CA19 2H086 BA15 BA33 BA55 2H111 BA39 4J037 AA30 FF08 EE08 EE08 FF08 EE08 EE08 EE08 EE08 EE08 EE08 EE08 EE08 EE08 EE08 EE08 EE08 EE08 EEFF EE08 EEFF EEEE EE08 EEEE FEEEEE EEEE EEEE CA06 DA02 EA34 EA35 EA42 GA06 GA24

Claims (8)

[Claims] 1. A colored image-forming composition comprising a phthalocyanine compound represented by the following general formula (I). [Chemical 1] In the general formula (I): R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R.
₁₃ and R ₁₆ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group,
Aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group,
Alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxy It represents a carbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, or an acyl group, each of which may further have a substituent. R
₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom or a substituted sulfamoyl group.
However, R ₂ and R ₃ , R ₆ and R ₇ , R ₁₀ and R ₁₁ , and R ₁₄ and R
_At least one of each of ₁₅ represents a substituted sulfamoyl group, and at least one of four or more substituted sulfamoyl groups has a substituent having 2 or more carbon atoms. And R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
The total number of carbon atoms of the substituents represented by ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ is 8 or more. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. 2. An ink comprising the colored image-forming composition according to claim 1. 3. A phthalocyanine represented by the general formula (I)
The compound is a phthalocyanine represented by the following general formula (II)
The compound according to claim 2, which is a compound.
Ku. [Chemical 2] In general formula (II): X₁, X₂, X₃, And X_FourRespectively
Independently, a hydrogen atom, a substituted or unsubstituted alkyl group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Cycloalkyl group, substituted or unsubstituted alkenyl
Groups, substituted or unsubstituted aralkyl groups, or substituted
Or an unsubstituted heterocyclic group. Y₁, Y₂, Y₃, And
And Y_FourAre independently substituted or unsubstituted ants.
Group. However, X₁, X₂, X₃, X_Four, Y₁,
Y₂, Y₃And Y_FourAt least one of which has 2 or more carbon atoms
Represents a substituent, and X₁, X₂, X₃, X_Four, Y₁, Y₂,
Y ₃And Y_FourWhen the total number of carbon atoms of the substituents represented by
is there. M has the same meaning as M in formula (I). l, m,
n and p each independently represent an integer of 1 or 2. 4. The ink according to claim 3, wherein the phthalocyanine compound represented by the general formula (II) is a phthalocyanine compound represented by the following general formula (III). [Chemical 3] In formula (III): W _{1 to} W ₂₀ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group,
Alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, 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, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo Group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group,
It represents a phosphoryl group or an acyl group, each of which may further have a substituent. However, W _{1 to} W ₅ , W _{6 to} W ₁₀ , W
₁₁ to _W-15, and W ₁₆ to _W-20 each set of the at least one set of the at least one two or more substituents carbon atoms in said set, and is expressed by W ₁ to _W-20 The total number of carbon atoms of the substituents is 8 or more. M, l, m, n and p have the same meanings as M, l, m, n and p in the general formula (II). 5. An ink jet ink, which is the ink according to any one of claims 2 to 4. 6. An image is formed on the image receiving material having an ink image receiving layer containing white inorganic pigment particles on a support using the ink according to any one of claims 2 to 5 or an inkjet ink. Characteristic inkjet recording method. 7. A method for improving ozone gas fading resistance of an image recorded matter, which comprises forming an image using the ink according to any one of claims 2 to 5 or an inkjet ink. 8. A phthalocyanine compound represented by the general formula (IV). [Chemical 4] In formula (IV): W _{1 to} W ₂₀ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group,
Alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, 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, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo Group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group,
It represents a phosphoryl group or an acyl group, each of which may further have a substituent. However, W _{1 to} W ₅ , W _{6 to} W ₁₀ , W
₁₁ to _W-15, and W ₁₆ to _W-20 are each independently, each have a substituent group having at least 2 carbon atoms, and, W ₁ total number of carbon atoms of the substituents represented by to _W-20 is 8 or more Is. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. l, m, n, and p each independently represent an integer of 1 or 2.