WO2004035691A1 - Phthalocyanine compounds for ink-jet recording, water-base green ink compositions containing the compounds, and colored prints made by using the same - Google Patents

Abstract

Water-soluble phthalocyanine compounds for ink-jet recording which have high-clarity hue suitable for ink-jet recording, can give prints excellent in fastness, and are excellent in shelf stability, that is, those represented by the general formula (1): (1) wherein B is a pyridoneazoanilino group represented by the general formula (2); and other symbols are each as defined in the description.

Description

 Specification

 TECHNICAL FIELD The present invention relates to a phthalocyanine compound for ink jet recording, an aqueous green ink composition containing the same, and a colored body obtained using the same.

 The present invention provides a green pigment composition and an aqueous green ink composition containing a water-soluble cyanine compound, a mixture of a water-soluble phthalocyanine compound and a yellow dye, and a green ink composition useful for a recording method using an ink-jet printer. It relates to a colored body with high sharpness. Background art

 Among the various color recording methods, in the recording method using an ink jet printer, which is one of the representative methods, various ink ejection methods have been developed. Recording is performed by adhering to a recording material (paper, film, cloth, etc.). This is because the recording head and the recording material do not come in contact with each other, so that there is no sound and the recording is quiet. In addition, it is rapidly becoming popular in recent years because of its small size, high speed, and easy colorization. However, significant growth is expected in the future. Of these, to record the image or character information on the computer display in color by ink jet printing, generally, yellow (Y), magenta (Μ), cyan (C), black (K ) Is represented by subtractive color mixing using the four color inks. To reproduce additively mixed images of red (R), green (G), and blue (B) as faithfully as possible with subtractive images, such as CRT displays, hues as close as possible to Y, M, and C standards It is desirable to have sharpness and sharpness.

In order to solve these problems, an ink jet printing method using seven color (Y, M, C, R, G, B, K) inks has been proposed (for example, Japanese Patent Application Laid-Open No. 2002-224161). However, since vat dyes (bat dyes) having soluble groups are used there, it is necessary to completely satisfy the market requirements in terms of hue, sharpness, fastness, and the like. Not reached. In addition, for conventional inkjet Even if Y, M, and C used as inks are mixed in advance and inks such as R, G, and B are used, the problem of poor clarity remains.

 On the other hand, conventional green dyes have been developed for use in inkjet type color filters, and a phthalocyanine compound (green dye) is described as a dye contained in an ink composition for one color filter. Also, a method for producing a green dye is described (for example, Japanese Patent Application Laid-Open No. 8-60052). In addition, an ink composition for a color filter containing a phthalocyanine-based anionic water-soluble green dye is also described (for example, JP-A-9-1291240).

 Further, the ink composition is required to be stable for long-term storage, to have a high density of printed images, and to be excellent in fastness such as water resistance, light resistance and gas resistance. Furthermore, with the recent spread of digital cameras, the opportunity to print images at home has also increased. Discoloration of images due to oxidizing gas in the air when storing the resulting prints is also viewed as a problem. Disclosure of the invention

 An object of the present invention is to provide a daline dye for ink jet recording which has a high solubility in water, has a hue and sharpness suitable for ink jet recording, and is more safe for humans, and an ink composition containing the same. Aim. The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have reached the present invention. That is, the present invention

 (1) In the form of the free acid, the following formula (1) '

[In the formula (1), Me represents Cu, Zn or Al, and Pc represents a phthalocyanine residue. A one _{NH 2; - NHCH 2 CH 2} OH; - N (CH 2 CH 2 OH) 2; -NHCH 2 COOH; one _{NHC 2 H 4 S 0 3 H} ; nitro group, Karupokishi group, nitrile group or a hydroxyl group Hue optionally substituted with Represents a nol residue. Hi represents 0 to 3, 0 represents 0 to 2, and a represents 1 to 4, and + 3 + a is 4 or less. B is the free acid form of formula (2)

(In the formula (2), R 2 is independently 1 H, 1 CH ₃ , 1 COOH, — NHCO CH ₃ , a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ₃ is 1 CONH ₂ , — CN Or one CH ₂ SO ₃ H, R ₄ is an alkyl group having 1 to 4 carbon atoms, one (CH ₂ ) _n C〇OH, one (CH ₂ ) _q S 03 H (q represents 1, 2 or 3) Or a hydroxyalkyl group having 1 to 3 carbon atoms, and n represents 0 to 2. Sulfonic acid, carboxylic acid, and hydroxyl group are all represented in free acid form. Represents a compound residue. A water-soluble phthalocyanine compound for ink jet recording represented by

(2) B is the following formula (3)

Wherein (3), R ₃ is one CONH _2, or - a _{CH 2 S 0 3 H, R} 4 is an alkyl group having 1 to carbon atoms 4, n represents each 0 or 1. (1) a water-soluble phthalocyanine compound for ink jet recording,

(3) The compound of the formula (1) is represented by the following formula (4)

[In the formula (4), Me represents Cu, and Pc represents a phthalocyanine residue. Represents 0 to 3, a represents 1 to 2, and α + a is 4 or less. ; ₃ one CONH _2, or represents an _{CH 2 S 0 3 H, R} 4 represents an alkyl group having 1 to 4 carbon atoms, n represents 0 or 1. The water-soluble phthalocyanine compound for ink jet recording according to (1), which is a compound represented by the formula (1):

 (4) a green inkjet recording composition comprising the water-soluble phthalocyanine compound for inkjet recording according to any one of (1) to (3),

 (5) (1) an ink jet recording green composition comprising a mixture of a water-soluble phthalocyanine compound for inkjet recording and a yellow dye according to any one of (3),

 (6) The ink jet recording green composition according to (5), wherein the yellow dye is a water-soluble pyridone azo compound represented by the following formula (5):

[In the formula (5), R i and R ₂ each independently represent 1 H, _CH ₃ , 1 C〇OH, 1 NHCO CH ₃ , a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ₃ represents 1 C ONH ₂ , one CN or —CH ₂ S 0 ₃ H, R ₄ is an alkyl group having 1 to 4 carbon atoms, — (CH ₂ ) _q COOH, — (CH ₂ ) _q S 0 ₃ H (q is 1 , 2 or 3) or a hydroxyalkyl group having 1 to 3 carbon atoms, n represents 0 to 3, and C represents a hydrogen atom, a substituent or a linking group, respectively. ] (7) The green composition for inkjet recording according to (6), wherein the formula (5) is the following formula (6):

Wherein (6), R ₃ one CONH _2, one CN or - a _{CH 2 S 0 3 H,;} 4 is an alkyl group having a carbon number of 1 - 4, one (CH ₂₎ QC_〇_OH one (CH ₂ ) _q S 0 ₃ H (q represents 1, 2 or 3) or a hydroxyalkyl group having 1 to 3 carbon atoms, n represents 0 to 3, C represents an amino group, an acetylamino group, -SO 2 H, or —SO ₃ H, or a group represented by the following formula (7), (8) or (9) as a free acid]

X- HN-

(7)

 Υ

(In the formulas (7), (8) and (9), X and Y each independently represent a chlorine atom, a substituted or unsubstituted amino group or a substituted or unsubstituted hydroxyl group. D ₂ is independently 1 H, 1 CH ₃ , 1 COOH, —NHCOCH ₃ , a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and D ₃ is 1 CONH ₂ , 1 CN or —CH ₂ S〇 ₃ H D ₄ represents an alkyl group having 1 to ₄ carbon atoms, — (CH ₂ ) _n C〇OH, — (CH ₂ ) _q S 03 H (Q represents 1, 2 or 3), or 1 to 3 carbon atoms. And n represents 0 to 3, respectively. (8) As the pigment component, the water-soluble phthalocyanine compound for inkjet recording according to any one of (1) to (3) or the ink jet recording according to any one of (5) to (7). An aqueous green ink composition for ink jet recording comprising a green composition, (9) a water-soluble phthalocyanine compound for ink jet recording according to any one of (1) to (3), (5) A method for producing an aqueous green ink composition for aqueous inkjet recording, comprising dissolving the green composition for inkjet recording according to any one of (7) to (11) in an aqueous medium;

 (10) In an ink jet recording method in which ink droplets are ejected according to a recording signal to perform recording on a recording material, the aqueous green ink composition for ink jet recording described in (8) is used as the ink composition. An ink jet recording method,

 (11) The inkjet recording method according to (10), wherein the recording material is an information transmission sheet.

 (1 2) The ink jet recording method according to (1 1), wherein the information transmission sheet is a surface-treated sheet.

 (13) A colored body colored with the aqueous green ink composition for inkjet recording according to (8),

 (14) The colored body of (13), which was colored by pudding

 (15) An ink jet printer loaded with a container containing the aqueous green ink composition for inkjet recording according to (8),

(16) A water-soluble phthalocyanine compound represented by the following formula (10) as a free acid:

(In the formula (10), Pc is a phthalocyanine residue, is 1 to 3, α is 1 to 4, α + α is 4 or less. Η is 0 to 2, R; ^ R ₂ Each independently represents a hydrogen atom or one C OOH, R ₃ represents one CN, — CH ₂ S〇 ₃ H or one C〇NH ₂ , and R ₄ represents one C ₂ H ₅ or — n—C ₄ H ₉ Represent each)

(17) The position of each substituent in CuPc is the 4-position of each benzene nucleus (4, 4 ', 4' 'or 4' '' position of the following formula (11)) The water-soluble phthalocyanine compound according to (16),

(18) An aqueous green ink composition for ink jet recording, comprising a water-soluble phthalocyanine compound as described in (16) or (17) as a dye component,

(19) A green composition for ink jet recording comprising a mixture of the water-soluble phthalocyanine compound according to (16) or (17) and a yellow dye. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, a sulfonic acid group, a hydroxyl group, and a carboxyl group are represented in a free acid form unless otherwise specified. The water-soluble phthalocyanine compound for ink jet recording of the present invention will be described. In the formula (1), the phenol residue which may be substituted with a nitro group, a carboxy group, a nitrile group, or a hydroxyl group of A is, for example, a 0-nitrophenol residue, a m-nitrophenol residue. Group, p-nitrophenol residue, 2,4-dinitrophenol residue, phenol residue of 2,4-dihydroxybenzoic acid, and phenol residue of 2,4-dihydroxybenzonitrile. 1 ^ 6. 11, 211 or 1 is preferred, with Cu being preferred in terms of fastness.

In the general formula (2), examples of the halogen atom for R ₁ R ₂ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group having 1 to 3 carbon atoms include, for example, methoxy group and ethoxy group. Group, η-propoxy group and isopropoxy group. The hydroxyalkyl group having a carbon number of 1-3 represented by R _4, 2-hydroxypropyl, 3-hydro Kishipuropiru group, 2-hydroxy E ethyl group and the like. Examples of the alkyl group having 14 to 14 carbon atoms include a methyl group, an ethyl group, an η-propyl group, an isopropyl group, an η-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group.

The bonding position of the azo group on the benzene ring is preferably 3-position relative to the bonding position of the phthalocyanine residue.

 The water-soluble phthalocyanine compound for ink jet recording of the present invention is particularly preferably a compound represented by the above formula (10).

Preferred combinations of R ~ in Formula (2), for example R丄is a hydrogen atom, R ₂ is a hydrogen atom, R ₃ is CONH ₂ or one CH ₂ S 0 ₃ H, with R ₄ is n- butyl is there. Further, n is 1, and the bonding position of the sulfonic acid group on the benzene ring is preferably 4-position relative to the bonding position of the phthalocyanine residue. The 4th position means that the position of the substituent on each benzene nucleus in CuPc is the 4, 4 ', 4 "or 4'" position of the following formula (11).

Specific examples of the compound represented by the formula (1) include, for example, the following compound No. • No. 18.

化合物 No.7

Compound No.7

11

Replacement form (Rule 26) Compound No.14 Compound N

Compound No.16 CuPc

Compound No. Π

Compound No.18

12

Replacement paper (Rule 26) Next, the yellow dye represented by the formula (5), which can be used in combination with the water-soluble phthalocyanine compound for ink jet recording of the present invention, if necessary, will be described. In the formula (5), examples of the halogen atom of R i, R ₂ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the alkoxy group having 1 to 3 carbon atoms, for example, a methoxy group Ethoxy group, n-propoxy group; and isopropoxy group. Examples of the alkyl group having 1 to 4 carbon atoms for R ₄ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. . Examples of C include an amino group, a sulfonic group, an acetylamino group, and the above formulas (7) to (9).

In the formulas (7) to (9), examples of the group that can be substituted for the amino group of X and Y include a hydroxyl group, a sulfonic group, and a phenyl group, and the phenyl group is a sulfonic acid group and an alkyl group. It may be replaced. Examples of the group which can be substituted with a hydroxyl group include an alkyl group. Specific examples of the formulas (7), (8) and (9) include groups represented by the following formulas (10) to (16).

式 （ 5)、 式 （6) で示される化合物で好ましいものとしては下記に示 す化合物 No. 1 9〜 29が挙げられる。

Preferred examples of the compounds represented by the formulas (5) and (6) include the compound Nos. 19 to 29 shown below.

 Compound No. 19

Compound No.20 Compound No.21

Compound No, 22

Compound No. 23

Compound ・^'24 H ₃ COCHNQ / ^S ° ^3H _CH3

 HO, O

C ₂ H ₅

Compound No.25

Compound No. 26

Compound No. 27

Compound No.28

Compound No.29 = \, S0 ₃ H

HO3S hi CH ₃

N == N- _f ^ ¾ _Sr -CONH ₂

 CI

C ₂ H _{5 The} phthalocyanine compounds represented by the formula (1), the formula (4) and the formula (10) are described in, for example, JP-A-8-60052 (0 064) to (0 083 ) Can be manufactured according to the manufacturing method described in (2).

In the phthalocyanine compounds represented by the formulas (1), (4) and (10), the phthalocyanine compound in which the position of the group substituted on the benzene nucleus on the phthalocyanine nucleus is at the 4-position is the respective phthalocyanine compound. A copper phthalocyanine having a sulfone group at the 4-position of the benzene nucleus on the mouth cyanine nucleus was produced, and the sulfonic acid was chlorided by a known method. It can be manufactured according to the manufacturing method described in (0 0 64) to (008 3) of the gazette. Copper phthalocyanines having a sulfonate group at the 4-position of the benzene nucleus on each phthalocyanine nucleus are described in, for example, Japanese Patent Application Laid-Open No. 2000-30309 (0 0 10) to (0 0 11), ( For example, 4-sulfophthalic acid or 4-sulfophthalic acid and anhydrous It is obtained by heating and reacting phthalic acid in a desired ratio in the presence of urea, a catalyst and a copper compound. The reaction temperature is usually 150 to 290 ° C at normal pressure, preferably 170 to 270 ° C. The reaction time varies depending on the reaction temperature, but is usually 1 to 8 hours. The number of sulfone groups can be adjusted by changing the molar ratio of the reaction between 4-sulfophthalic acid and phthalic anhydride.

 The pyridazo compounds represented by the formulas (5) and (6) can be produced, for example, as follows. That is, when 1 C in the formula (5) or (6) is a substituent, it is obtained by diazotizing an aromatic amine and then coupling it to a hydroxypyridone. Each substituent may be introduced before or after subjecting to the diazotization coupling reaction, but it is preferable to introduce each substituent before subjecting to the diazotization coupling reaction.

 In Formula (5) or (6), when 1 C is a substituent, a water-soluble pyridazo compound into which the substituent is introduced as 1 C is used. In general, an amino group is introduced by using an aromatic amine having an acetylamino group as C in the formula, and hydrolyzing after diazotized coupling with the pyridone azo compound.

 When X and Y are both chlorine atoms in the pyridone azo compound having a linking group represented by the formula (7), by condensing cyanuric chloride with the above-mentioned water-soluble pyridone azo compound into which an amino group has been introduced. can get. When X and Y are groups other than chlorine, they can be obtained by condensing cyanuric chloride with HX, HY, and the water-soluble pyridone azo compound into which the amino group has been introduced in any order. When X and Y are groups other than chlorine and both X and Y are hydroxyl groups, after condensing cyanuric chloride with the above-described water-soluble pyridone azo compound having an amino group introduced thereinto, alkali hydroxide is added. It is obtained by performing hydrolysis using When one of X and Y is a hydroxyl group, condensation of cyanuric chloride with HX or HY, and the above-mentioned water-soluble pyridone azo compound into which an amino group has been introduced, in any order, followed by hydrolysis using alkali hydroxide Is obtained.

In the pyridone azo compound having a linking group represented by the formula (8), when Y is a chlorine atom, cyanuric chloride and the above-described water-soluble pyridine group into which the above amino group has been introduced. It is obtained by condensing two equivalents of a lidazo compound. When Y is a group other than chlorine, it can be obtained by condensing cyanuric chloride with HY and two equivalents of the water-soluble pyridone azo compound into which the above amino group has been introduced in an arbitrary order. When Y is a group other than chlorine and Y is a hydroxyl group, condensation of cyanuric chloride and 2 equivalents of the above-mentioned water-soluble pyridone azo compound into which an amino group has been introduced is carried out in an arbitrary order, followed by hydroxylation. It is obtained by carrying out hydrolysis using an alcohol. The water-soluble pyridazo compounds into which two equivalents of the above amino groups have been introduced may be the same or different.

Among the pyridazo compounds having a linking group represented by the formula (9), when both Y are chlorine atoms, two equivalents of cyanuric chloride and ethylenediamine and the water-soluble pyridone azo compound 2 into which the above-mentioned amino group is introduced. It is obtained by condensing the equivalents in any order. When one Y is a chlorine atom and the other Y is a group other than chlorine, 2 equivalents of cyanuric chloride and 1 equivalent of ethylenediamine, 1 equivalent of HY, and a water-soluble pyridone azo having the above-described amino group introduced thereinto. It is obtained by condensing two equivalents of the compound in any order. When one Y is a chlorine atom and the other Y is a group other than chlorine, and the Y is a hydroxyl group, the water-soluble pyridazole having two equivalents of cyanuric chloride, ethylenediamine and the amino group described above is introduced. The compound is obtained by condensing two equivalents of the compound in an arbitrary order, followed by mild hydrolysis using an alkali hydroxide. When both Y are groups other than chlorine, 2 equivalents of cyanuric chloride, 2 equivalents of ethylenediamine, 2 equivalents of HY, and 2 equivalents of a water-soluble pyridazo compound into which the above-described amino group has been introduced are condensed in any order. It is obtained by doing. HY for two equivalents may be the same or different. When both Y are groups other than chlorine and both Y are hydroxyl groups, two equivalents of cyanuric chloride and two equivalents of ethylenediamine and the above-described water-soluble pyridazo compound into which the amino group has been introduced are optionally added. After condensation in order, it can be obtained by carrying out strong hydrolysis using hydroxide hydroxide. Two equivalents of the above-mentioned amino-group-introduced pyridone azo compound having an amino group may be the same or different. May be.

Further, when one C in the formula (5) or the formula (6) is a linking group, it can also be produced as follows. That is, it is obtained by diazotizing an aromatic diamine to condensed cyanuric chloride after condensing it, and coupling it to hydroxypyridones.In this case, cyanuric chloride may be uncondensed cyanuric chloride or chloride after primary condensation. It may be cyanur or cyanuric chloride after secondary condensation. The water-soluble phthalocyanine compound for ink jet recording of the present invention exists in the form of a free acid or a salt thereof. In the present invention, the salt can be used as an alkali metal salt, an alkaline earth metal salt, an alkylamine salt, an alkanolamine salt or an ammonium salt. Preferred are alkali metal salts such as sodium salt, potassium salt, and lithium salt; alkanol salts such as monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, and triisopropanolamine salt. Luamine salts and ammonium salts. In addition, as a method of preparing a salt, for example, sodium salt is added to the reaction solution obtained above, or a cake or a dried product dissolved in water, salted out, and filtered to obtain sodium salt as a wet cake, and the wet cake is again obtained. After dissolving in water, hydrochloric acid is added to adjust the pH to 1-2, and the crystals obtained are filtered to obtain the free acid (or a part of it as a sodium salt). Next, the dye in the form of the free acid is dissolved or suspended in water, and a base corresponding to the target salt, for example, an amine or an alkali metal compound other than sodium, is added and dissolved to form a solution of each salt. can get. From the solution, the salts other than the sodium salt can be obtained by precipitating, filtering, and drying each salt by a conventional method. Of these salts, preferred are the lithium and sodium salts. The mixing ratio of the phthalocyanine compound for inkjet recording of the present invention and the pyridone azo compound represented by the formula (5) or (6) is, for example, 100 to 5 for the phthalocyanine compound and 0 to 95 for the pyridonazo compound. , Preferably Is a pyridone azo compound 20 to 50 with respect to a phthalocyanine compound 80 to 50. The yellow dye other than the pyridoneazo compounds represented by the formulas (5) and (6) is preferably a water-soluble yellow direct dye or reactive dye having a maximum absorption wavelength in the visible light region of 41 O nm or less. And direct dyes are preferred. Particularly preferred are I. Direc t Yellow 132, 120 and U2. These yellow dyes are used in the form of a free acid or a salt thereof. The salt exchange may be performed in the same manner as described above.

 The mixing ratio of the phthalocyanine compound for inkjet recording of the present invention to the yellow dye other than the pyridoneazo compound represented by the formula (5) or (6) is, for example, 100 to 5 for the phthalocyanine compound and 0 for the yellow dye. ~ 95 (weight ratio). Preferably, the phthalocyanine compound is 80 to 40, and the yellow dye is 20 to 60 (weight ratio). The ink jet recording green composition of the present invention is suitable for dyeing natural and synthetic fiber materials or blended products, and these ink jet recording green compositions are remarkably suitable for producing writing inks and recording liquids. ing.

The reaction liquid of the phthalocyanine compound for ink jet recording of the present invention and, if necessary, a yellow dye used together can be used directly for producing a recording ink composition. However, it can be isolated from the reaction solution, dried, for example, spray-dried, and then processed into an ink composition. The recording ink composition of the final product usually contains 0.1 to 20% by weight, more preferably 1 to 5% by weight, and still more preferably 2 to 10% by weight of the green dye of the present invention in an aqueous solution. _C The ink composition of the present invention may contain 0 to 30% by weight of a water-soluble organic solvent and 0 to 5% by weight of an ink preparation. The aqueous green ink composition for inkjet recording of the present invention comprises a phthalocyanine compound alone, a mixture of a phthalocyanine compound and a pyridoneazo compound. Or a green dye consisting of a mixture of a phthalocyanine compound and a yellow dye dissolved in water or an aqueous solvent (water containing a water-soluble organic solvent). Examples of the water-soluble organic solvent that can be used in the present invention include C 1, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol. Carboxylic acid amides such as C4 alkanol, N, N-dimethylformamide or N, N-dimethylacetamide, lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1 Cyclic ureas such as 2,3-dimethylimidazolidine-1-one or 1,3-dimethylhexahydropyrimido-2-one, ketones such as acetone, methylethylketone, 2-methyl-2-hydroxypentane-one Or cyclic ethers such as keto alcohol, tetrahydrofuran, and dioxane, ethylene glycol, 1,2- or 1,3-propylene glycol, 1 2 — or 1,4 monobutylene glycol, 1,6 hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc. (C2-C6) Monomers, oligomers or polyalkylene glycols having alkylene units or polyols (triols) such as polyalkylene glycol or thioglycol, glycerin, hexane-1,2,6-triol, ethylene glycol monomethyl ether Or ethylene dalicol monoethyl ether, diethylene dalicol monomethyl ether or diethylene dalicol monoethyl ether, or triethylene daryl monomethyl ether or triethylene glycol monoethyl ether (C 1 -C 4) alkyl ethers of polyhydric alcohols such as ether, heptyl lactone or dimethyl sulfoxide.

In the composition of the present invention, preferred as the water-soluble organic solvent are 2-piperidone, N-methyl-1-pyrrolidone, mono-, di- or triethylene glycol, and dipropylene glycol, more preferably 2-pyrrolidone. Don, N-methyl-1-pyrrolidone and diethylenedalicol. These water-soluble organic solvents are used alone or as a mixture. - Examples of the ink preparation agent include an antiseptic / antifungal agent, a pH adjusting agent, a chelating agent, an antibacterial agent, a water-soluble ultraviolet absorber, a water-soluble polymer compound, a dye dissolving agent, a surfactant and the like. Examples of preservatives and fungicides include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloallyl sulfone'-based, eodopropagyl-based, N-octaloalkylthio-based, nitrile-based, pyridine-based, and 8-oxyquinoline-based , Benzothiazole, isothiazoline, dithiol, pyridinoxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate And brominated indanone compounds, benzyl bromacetate compounds, and inorganic salt compounds. Examples of the organic halogen-based compound include sodium pentachlorophenol, examples of the pyridine oxide-based compound include sodium 2-pyridinethiol-l-oxide, and examples of the inorganic salt-based compound include anhydrous sodium. Sodium acetate may be mentioned. Examples of the isothiazoline-based compounds include 1,2-benzisothiazoline-3-one, 2-n-octyl-4 monoisothiazoline-3-one, and 5-chloro-2-methyl-4-isothiazoline-3. —One, 5-chloro-2-methyl-4 monoisothiazoline—3one magnesium chloride, 5—chloro-2-methyl-4-isothiazoline-13—oncalcium chloride, 2-methyl-4-isothiazoline—3—on calcium chloride And the like. Other preservatives and fungicides include sodium sorbate and sodium benzoate.

As the pH adjuster, any substance can be used as long as it can control the pH of the ink within the range of 8.0 to 11.0 without adversely affecting the prepared ink. For example, alkanolamines such as diethanolamine and triethanolamine, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, or lithium carbonate, sodium carbonate, Examples include alkali metal carbonates such as potassium carbonate. Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium triacetate triacetate, sodium hydroxyethylethylendiaminetriacetate, sodium diethylenetriaminepentaacetate, ゥ Sodium ramyldiacetate. Examples of the protective agent include acid sulfite, sodium thiosulfate, ammonium thioglycolic acid nitrite, diisopropylammonium nitrite, erythritol tetranitrate, dicyclohexylammonium nitrite, and the like. Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone and sulfonated benzotriazole. Examples of the water-soluble polymer compound include polyvinyl alcohol, a cellulose derivative, polyamine, and polyimine. Examples of the dye dissolving agent include urea, ε-force prolactam, ethylene carbonate and the like. Examples of the surfactant include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant. Examples of anionic surfactants include alkyl sulfocarbonates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, hydroxyamino acids and salts thereof, hydroxymethyltaurine salts, and alkyl sulfate polyoxylates. Alkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid stone, castor oil sulfate, lauryl alcohol sulfate, alkylphenol-type phosphate, alkyl-type phosphate, alkylaryl sulfone hydrochloride, getyl sulfo And succinate, and octyl sulfosuccinate dioctyl sulfosuccinate. Examples of the cationic surfactant include a 2-vinylpyridine derivative and a poly (vinylvinylpyridine) derivative. Examples of amphoteric surfactants include betaine lauryl dimethylaminoacetate, 2-alkyl-hydroxypropyloxymethyl hydroxybetaine, coconut oil fatty acid amidopropyldimethylaminoacetate, and polyoctyl polyaminoethyl ester. There are lysine and other imidazoline derivatives. Examples of the nonionic surfactant include polyoxyethylene nonyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, Ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and polyoxyarylalkyl alkyl ether, poly Acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiolate, polyoxyethylene monooleate, polyoxyethylene Esters such as stearate, 2,4,7,9-tetramethyl-15-decine-14,7-diol, 3,6-dimethyl-4, one-year-old cutin-3,6-diol, 3,5-dimethyl-1 Acetylene glycols such as 1-hexin-3-ol (for example, Surfinol 104, 104 PG50, 82, 465, and Olfin STG manufactured by Nissin Chemical Co., Ltd.), etc. Can be These ink preparations are used alone or as a mixture. The aqueous green ink composition for ink jet recording of the present invention comprises a green dye comprising a phthalocyanine compound alone, a mixture of a phthalocyanine compound and a pyridoneazo compound, or a mixture of a phthalocyanine compound and a yellow dye, in water or the above aqueous solvent (water-soluble organic solvent). Solvent-containing water) together with the ink preparation agent and the like.

 When this aqueous green ink composition for ink jet recording is used as an ink for an ink jet printer, the content of a phthalocyanine compound or a pyridone azo compound, and the content of inorganic substances such as metal cation chlorides and sulfates as known yellow dyes. It is preferable to use one having a small amount, and the standard of the content is, for example, about 1% by weight or less in the dye. In order to produce a phthalocyanine compound or a pyridoneazo compound having a small amount of inorganic substances, desalting may be performed by a usual method such as a method using a reverse osmosis membrane. When desalting the green dye mixed with the yellow dye, each may be subjected to desalting treatment and then mixed, or may be mixed and then desalted. Is desirably mixed after mixing.

In the production method of the present invention, the order of dissolution is not particularly limited. It may be pre-dissolved in water or the above-mentioned aqueous solvent (water containing a water-soluble organic solvent), and then dissolved by adding an ink preparation, or after dissolving the green dye of the present invention in water, A solvent and an ink preparation may be added and dissolved. Ma The order may be different from that described above, or an aqueous solvent and an ink preparation may be added to a reaction solution of the green dye of the present invention or a solution that has been subjected to a desalination treatment using a reverse osmosis membrane to form an ink composition. May be manufactured.

 In producing the ink of the present invention, the order of dissolving each drug is not particularly limited. In preparing the ink, the water to be used is preferably an ion-exchanged water or a water with few impurities such as distilled water. Further, if necessary, fine filtration may be performed using a membrane filter or the like to remove impurities, and when used as an ink for an ink jet printer, it is preferable to perform fine filtration. The pore size of a filter for performing microfiltration is usually 1 micron to 0.1 micron, preferably 0.8 micron to 0.2 micron.

 The recording ink composition containing the water-soluble phthalocyanine compound of the present invention is suitable for use in printing, copying, marking, writing, drafting, stamping, or a recording method, particularly an ink jet printing method. In this case, a high-quality green print having good resistance to water, sunlight, ozone and friction is obtained. In addition, the water-soluble phthalocyanine compound of the present invention may be further mixed with a well-known and commonly used dye such as yellow or cyan to obtain a desired green color tone.

 The colored body of the present invention is colored with the above-mentioned compound of the present invention. The material to be colored is not particularly limited, and examples thereof include, but are not limited to, paper, fiber and cloth (cellulose, nylon, wool, and the like), leather, and base materials for color filters. As a coloring method, a method using an ink jet printer is optimal, but it can also be applied to, for example, a printing method such as a dip dyeing method, a printing method, and a screen printing method.

Examples of the recording material to which the ink jet recording method of the present invention can be applied include a sheet for transmitting information such as paper and a film, a fiber and leather. The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet provided with an ink receiving layer on these substrates. The ink receiving layer is formed, for example, by impregnating or coating the above-mentioned base material with a cationic polymer, or by using inorganic fine particles capable of absorbing pigments such as porous silica, alumina sol or special ceramics in polyvinyl alcohol or polyvinyl pyrrolidone. Etc. hydrophilic It is provided by coating on the surface of the base material together with the hydrophilic polymer. A sheet provided with such an ink receiving layer is usually called a special ink jet paper (film) or a glossy paper (film), such as a pictorico (manufactured by Asahi Glass Co., Ltd.), a color BJ paper, a color BJ photo film sheet. , Professional Photo Paper (both from Canon Inc.), Color Image Jet Paper (from Sharp Corp.), PM Photo Paper, Super Fine Dedicated Glossy Film (all from Epson Corp.) , And Pictafine (manufactured by Hitachi Maxell, Ltd.). Of course, it can also be used for plain paper.

 In the ink jet recording method of the present invention, the aqueous green ink composition for ink jet recording of the present invention can be used in combination with a yellow ink composition, a magenta ink composition, a cyan ink composition and, if necessary, a black ink composition.

The ink composition of each color is poured into each container, and this container is set (loaded) at a predetermined position of an ink jet printer, similarly to the container containing the aqueous green ink composition for ink jet recording of the present invention. , used. '' In order to record on a recording material by the ink jet recording method of the present invention, for example, a container containing the above ink composition is set at a predetermined position of an ink jet printer, and recording is performed on the recording material by an ordinary method. Just fine. Examples of the ink jet printer include a piezo printer using mechanical vibration and a bubble jet (registered trademark) printer using bubbles generated by heating. The ink jet recording green ink composition of the present invention has a sharp dull color, and particularly has a high sharp hue on glossy ink jet paper. It is also very safe for humans. When used with other yellow and cyan inks, it is possible to produce a wide visible color tone that cannot be obtained with the green color resulting from the mixture of normal cyan ink and yellow ink. . The green ink composition for ink jet recording according to the present invention does not precipitate or separate during storage. Further, when the green ink composition for ink jet recording according to the present invention is used in ink jet printing, the ejector (ink head) is not blocked. The green ink composition for ink jet recording according to the present invention does not change its physical properties even under constant recirculation for a relatively long time by a continuous ink jet printer or intermittent use by an on-demand ink jet printer. . Example

 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the text, “parts” and “%” are based on weight unless otherwise specified. Example 1

 (Method of synthesizing compound No. 1)

 (1) A solution obtained by dissolving 23.0 parts of 4-acetylamino-2-aminobenzenesulfonic acid in 40 parts of water with weak alkalinity, adding 7.5 parts of sodium nitrite and dissolving, The mixture was poured into 5% hydrochloric acid (220 parts) cooled to 5 ° C while adding ice at 5 ° C or less, and stirred for 1 hour to obtain 400 parts of a diazo liquid.

 (2) 23.5 parts of 1-butyl-3-forcerubamoyl-6-hydroxy-4-methyl-2-pyridone 24.0 parts was dissolved in 420 parts of water with a weak force, and then cooled to 10 ° C with ice. A 10% aqueous solution of sodium carbonate and 400 parts of the diazo solution of (1) were simultaneously added at pH 8 and at a liquid temperature of 10 ° C or lower while adding ice. After heating to 2, the mixture was stirred at PH 8 and the same temperature for 12 hours to complete the reaction.

(3) After heating the reaction solution of (2) to 80 ° C, 760 parts of 35% hydrochloric acid was added, and the mixture was further heated to 95 ° C. At this time, the hydrochloric acid concentration was 9.5% by volume. After stirring for 6 hours, the reaction was completed. After cooling to room temperature, 360 parts of sodium chloride was added to precipitate crystals, which was filtered. The crystals were washed with a 10% aqueous sodium chloride solution, dried and dried to obtain the following compound ( 0 1) 35.3 parts were obtained.

(4) While stirring in 92.0 parts of chlorosulfonic acid, 11.52 parts of copper phthalocyanine was added at 70 ° C or less, heated to 140 ° C, and reacted at the same temperature for 4 hours. After the reaction, the reaction solution was cooled, and the obtained reaction solution was poured into 400 parts of ice water to decompose residual chlorosulfonic acid. The precipitated crystals were filtered and washed with 130 parts of ice water to obtain 85.5 parts of a wet cake.

 (5) In 100 parts of ice water, 42.7 parts of the wet cake obtained in (4) (0.1 mol) were added, and the mixture was stirred and dispersed at 5 ° C or lower for 30 minutes. Water 45

4.45 parts (0.01 mo 1 minute) of the compound (01) was added to 0 parts and dissolved at 50 ° C. The solution was filtered, and the filtrate was cooled to 5 ° C. and poured into the dispersion. A 5% aqueous sodium hydroxide solution was neutralized to pH 8.5 at a liquid temperature of 5 ° C. or lower while adding ice. After stirring under the same conditions for 1 hour, the mixture was heated to 25 ° C, further stirred at H8.5 for 4 hours, heated to 50 ° C, and stirred for 1 hour. Sodium chloride is gradually added to the completely dissolved reaction solution until crystals precipitate, and the same amount of sodium chloride is added, and the crystals are filtered.The crystals are washed with a 20% aqueous sodium chloride solution and dried. Thus, 11.0 parts of a compound No. 1 (maximum absorption wavelength in water = 414 nm 667 nm) was obtained. Example 2

The phthalocyanine compound represented by Compound No. 1 obtained in Example 1 and Compound No. 19 (synthesized by Reference Example 1) were mixed, and a green dye composition (maximum absorption wavelength in water = 4 1) 8 nm, 668 nm). The mixing ratio is Compound No. 1940 parts to Compound No. 160 parts. Example 3 The phthalocyanine compound represented by Compound No. 1 obtained in Example 1 and Compound No. 20 (synthesized according to Reference Example 2) were mixed to obtain a green dye composition. The mixing ratio was such that Compound No. 160 was mixed with Compound No. 204 at a mixing ratio to obtain a green dye composition (maximum absorption wavelength in water = 19 nm, 668 nm). Example 4

A phthalocyanine compound represented by Compound No. 1 obtained in Synthesis Example 1 and Compound No. 21 (synthesized according to Reference Example 3) were mixed, and a green dye composition (maximum absorption wavelength in water = 414) nm, 668 nm). The mixing ratio was Compound No. 160 to Compound N 0.2 140. Example 5

The phthalocyanine compound represented by the compound No. 1 in Example 1 and a yellow direct dye (C.I. Direct Yellow 13) (the following formula (02)), the maximum absorption wavelength in water = 406 nm ) Were mixed to obtain a green dye (maximum absorption wavelength in water = 406 nm, 671 nm). As for the mixing ratio, C.I.DirecctYellow1332 is 30 for compound No.170.

Example 6—10

 (A) Preparation of the ink.

Using the compounds or compositions obtained in Examples 1, 2, 3, 4, and 5 above, liquids having the compositions shown in Table 2 were prepared, and each ink was obtained by filtration through a 0.45 m membrane filter. Thus, an aqueous ink composition for recording was obtained. Water used was ion-exchanged water. The pH of the ink composition was pH = 6-9, Water and sodium hydroxide were added to make the total amount 100 parts. Tests using the compound obtained in Example 1 were performed in Example 6, tests using the composition obtained in Example 2 were performed in Examples 7 and tests using the composition obtained in Example 3 were performed. The test using the composition obtained in Example 8 and Example 4 is referred to as Example 9, and the test using the composition obtained in Example 5 is referred to as Example 10. Table 1 (ink composition)

(B) Inkjet printing

 Plain paper (purine paper A4TLB5A4S (manufactured by Canon Inc.)) using an inkjet printer (BJ-S630 manufactured by Canon Inc.). Glossy paper with a dye receiving layer ( Inkjet recording was performed on three types of professional photo papers manufactured by Canon Inc. and PM Photo Paper KA 420 PSK manufactured by Epson Corporation. Hereinafter, as a comparative test, an ink was prepared so as to have the same print density as that of the ink of Example 1 and evaluated. Comparative Example 1

C. I. Direct B 1 u, which is widely used as a cyan dye for ink jet recording instead of the mixture obtained in the examples for comparison Except for mixing 2.5 parts of e199 with 2.5 parts of C.I.D irect Yellow 13 which is widely used as yellow dye for ink jet recording, and toning it. An ink was prepared and subjected to inkjet recording in the same manner as in Example 6, and the recorded image was evaluated.

As a result of various studies, the mixing ratio was selected to be 50:50, where the hue of the recorded image was close to that of the example.

(C) Evaluation of recorded image

 1. Hue evaluation

 1-1. Hue evaluation on glossy paper

 Hue and clarity of recorded image: Recording paper color measurement system (GRETAG SP

M50: manufactured by GRETAG), and the L * .a "and b values were calculated. The sharpness was determined by the chromaticity (a) when the L * value (brightness) of each recording paper was approximately matched. * b *) from the C * = ((a *) was calculated ^{2 + (b *) 2)} 1/2.

Table 2 shows the results of the hues of the Mitsuzawa paper (two types) of Example 6, Example 7, Example 8, Example 9, Example 10, and Comparative Example 1.

Table 2

表 2より、 本発明の実施例 6 (フタロシアニン化合物）、 実施例 7 〜 9 (フタロシアニン化合物とピリ ドンァゾ化合物との混合物）、 実施例 1 0 (フタロシアニン化合物と黄色直接染料との混合物） は、 比較例 1よりも 非常に鮮明性が高い色相であることがわかる。

From Table 2, it can be seen that Example 6 (phthalocyanine compound), Examples 7 to 9 (mixture of phthalocyanine compound and pyridoneazo compound) and Example 10 (mixture of phthalocyanine compound and yellow direct dye) of the present invention are comparative examples. It can be seen that the hue is much higher in sharpness than in Example 1.

1-2. Hue evaluation on plain paper

In the same manner as described above, Table 3 shows the results of hues of the plain papers of Example 6, Example 7, Example 8, Example 9, Example 10 and Comparative Example 1. Table 3

表 3より、 実施例 6 (フタロシアニン化合物）、 実施例 7〜 9 (フタ口 シァニン化合物とピリ ドンァゾ化合物との混合物）、 実施例 1 0 '(フタ口 シァニン化合物と黄色直接染料との混合物） は、 普通紙に記録画像した色 相が、 比較例 1より非常に鮮明性が高いことがわかる。

From Table 3, it can be seen that Example 6 (phthalocyanine compound), Examples 7 to 9 (mixture of phthalocyanine compound and pyridoneazo compound), and Example 10 '(mixture of phthalocyanine compound and yellow direct dye) It can be seen that the hue recorded on plain paper was much higher than in Comparative Example 1.

(D) Xenon light fastness test of recorded images

 A test piece printed on glossy paper made by Epson was irradiated for 50 hours at 0.36 W / square meter of illuminance using Xenon Zeaomei Ci 400 (AT LAS), before and after the test. Was measured. The results are shown in Table 4.

(E) Ozone resistance test of recorded images

A test piece printed on Epson glossy paper was introduced into an ozone weather meter using a humidifier, and an ozone weather meter (type OMS-H manufactured by Suga Test Instruments Co., Ltd.) was used to maintain a humidity of 60%. The sample was allowed to stand for 2 hours at a temperature of about 35 ° C and an ozone concentration of 12 ppm, and the color difference (ΔΕ) before and after the test was measured. The results are shown in Table 4. Table 4

表 4より、 実施例 6は、 比較例 1より耐オゾン性が強いことがわかる。 実施例 9は、 比較例 1より耐光性、 耐オゾン性が強いことがわかる。

Table 4 shows that Example 6 has higher ozone resistance than Comparative Example 1. It can be seen that Example 9 has stronger light resistance and ozone resistance than Comparative Example 1.

 From Tables 2 to 4, the phthalocyanine compound for ink jet recording of the present invention, the mixture of the phthalocyanine compound and the pyridoneazo compound, or the green ink using the phthalocyanine compound and the yellow dye have a very sharp hue. It can be seen that this is a very excellent green color ink with high ozone fastness. Example 11

 (Synthesis example 2)

 (Synthesis example of compound No. 30 in which the position of substituent is 4)

 (1) According to the method described in (0 209) of Japanese Patent Application Laid-Open No. 2000-300 309, the 4-position (4, 4 ', 4 ,,, 4 "') of each benzene nucleus ), A sulfo copper phthalocyanine having a total of four sulfone groups was synthesized.

To a four-necked flask equipped with a cooling tube, add 40 parts of sulfolane, raise the temperature to 180 ° C in 1 hour, and add 40 parts of 4-sulfophthalic acid, 4.5 parts of ammonium chloride, 5.5 parts of urea, 0.5 parts of ammonium molybdate and 6 parts of copper (II) chloride were added, and the mixture was stirred at the same temperature for 6 hours. After the reaction solution was cooled to 40 ° C., the target substance was filtered with Nutsche, and washed with 400 parts of methanol. Subsequently, 300 parts of water was added to the obtained wet cake, the pH was adjusted to 10 with a 48% aqueous sodium hydroxide solution, and the mixture was stirred at 80 ° C for 1 hour. While stirring, a 35% aqueous hydrochloric acid solution was added to adjust the pH to 3, and 80 parts of sodium chloride was gradually added thereto. The precipitated crystals were collected by filtration and washed with 150 parts of a 20% saline solution to obtain 90 parts of a wet cake. Subsequently, 210 parts of methanol was added and the mixture was stirred for 1 hour to precipitate. The crystals are separated by filtration, washed with 300 parts of Ί0% methanol aqueous solution and dried, and a total of sulfone groups are added at the 4th position (4, 4 ′, 4 ″, 4 ″ ″) of each benzene nucleus. 4 2. 9 parts of sulfo copper phthalocyanine having 4 were obtained as blue crystals.

 (2) Chlorosulfonic acid 7.8.7 parts of the compound obtained in (1) was gradually charged at 70 ° C or lower with stirring in 2 parts of 7.8.7 parts for 4 hours at 130 ° C. The reaction was performed. After the reaction solution was cooled to 80 ° C, 23.8 parts of thionyl chloride was gradually added dropwise, and the reaction was carried out at the same temperature for 2 hours. The resulting reaction solution was poured into 450 parts of ice water to decompose the remaining chlorosulfonic acid and thionyl chloride. After removing the sulfurous acid in the liquid with a hydrogen peroxide solution, the precipitated crystals were filtered to obtain 41.9 parts of a wet cake.

(3) To 100 parts of ice water, the {4.1.9} [5 (0.0 lmo 1 minute)] of the cake obtained in (2) was added, and the mixture was stirred and dispersed at 5 ° C or lower for 30 minutes. 6.650 parts (0.015 mol) of the compound (01) was added to 450 parts of water and dissolved at 50 ° C. The solution was filtered and the filtrate was cooled to 5 and poured into the dispersion. A 5% aqueous sodium hydroxide solution was added at a liquid temperature of 5 ° C or lower while adding ice; After stirring under the same conditions for 1 hour, heat to 25 ° C, further stir at pH 8 for 1 hour, heat to 35 ° C, further stir at pH 8 for 1 hour, heat to 60 ° C, Stir for 1 hour. Sodium chloride is gradually added to the completely dissolved reaction solution until crystals precipitate, and the same amount of sodium chloride is added. The crystals are filtered, dried and dried to obtain a compound of No. 30 (benzene nucleus of phthalocyanine nucleus). Compound having a substituent bonded to the 4-position) (Maximum absorption wavelength in water: 4 16 nm, 634 nm) 10.4 parts were obtained.

Example 1 2

The compound obtained in Example 11 was mixed with the compound of No. 20 (synthesized according to Reference Example 2) to obtain a green dye composition (maximum absorption wavelength in water: 421 nm, 634 nm). . The mixing ratio is 50 for the compound of No. 30 and 50 for the compound of No. 20. Example 13

The compound of No. 30 obtained in Example 11 and C. I. Direct Yellow 1332 represented by compound (02) were mixed with each other to give a green dye composition (maximum in water). Absorption wavelengths of 407 nm and 634 nm) were obtained. The mixing ratio of the compound of No. 30 is 60, and the mixing ratio of C. I. Direcct Ye1 ow 132 is 40. Preparation of ink

Using the compounds or compositions obtained in Examples 11, 12, and 13, the aqueous ink compositions for ink jet recording were obtained by the method according to the above-mentioned (A) ink preparation. The test using the compound obtained in Example 11 was performed in Example 14 and the test using the composition obtained in Example 12 was performed using the mixture obtained in Example 15 and Example 13. Example 16 is performed. (B) Inkjet printer Printing was performed in the same manner as described in Lint, and the hue was evaluated in the same manner as described in (C) Evaluation of recorded image. Example 14, Example 15 and Example

Table 5 shows the results of hues on 16 glossy papers (2 types), and Table 6 shows the results of hues on plain paper. Table 5

実施例 1 4、 1 5、 1 6は、 表 2 記載の比較例 1よりも鮮明性が高い 色相であることがわかる。 表 6

It can be seen that Examples 14, 15, and 16 have higher hues than Comparative Example 1 shown in Table 2. Table 6

実施例 1 4、 1 5、 1 6は普通紙に記録画像した色相が、 表 3に記載の比 較例 1よりも鮮明性が高いことがわかる。 下記 （F) の方法によりオゾン耐性試験を行い、 結果を表 7に示した。 (F) 記録画像のオゾン耐性試験一 2

It can be seen that in Examples 14, 15, 15 and 16, the hues recorded on plain paper had higher clarity than Comparative Example 1 shown in Table 3. An ozone resistance test was performed by the method (F) below, and the results are shown in Table 7. (F) Ozone resistance test of recorded images 1 2

 Using a test piece printed on glossy paper manufactured by Epson, using an ozone weather meter (model OMS-HS manufactured by Suga Test Instruments Co., Ltd.) for 2 hours at a temperature of about 40 ° C, a humidity of 55% RH, and an ozone concentration of 3 ppm The color difference (ΔΕ) was measured before and after the test. Table 7

表 7より、 実施例 6、 4、 1 5、 1 6は比較例 1よりもオゾン耐性が 強いことがわかる。 参考例 1 (化合物 No. 1 9の合成）

Table 7 shows that Examples 6, 4, 15, and 16 have higher ozone resistance than Comparative Example 1. Reference Example 1 (Synthesis of Compound No. 19)

 Under the same reaction conditions as in Example 1 using 23.0 parts of 4-acetylamino-2-sulfonic acid and 2-8.2 parts of 1-ethyl-3-sulfomethyl-6-hydroxy-4-methyl-2-pyridone as starting materials 40.1 parts of compound (04) were obtained.

(2) Add 9.225 parts (0.05 mol) of cyanuric chloride to 70 parts of ice water. The mixture was stirred and dispersed at 5 or less for 1 hour. Dissolve 46.8 parts of the compound (04) obtained in the above (1) in 150 parts of water, and add dropwise to the above dispersion at 5 ° C or lower while adding ice over 1 hour. did. Further, a 10% aqueous sodium carbonate solution was added dropwise at 5 ° C. or lower over 1 hour while adding ice, and the mixture was neutralized to pH 7.0. After reacting for 1 hour under the same conditions, the mixture was heated to 60 ° C while neutralizing to pH 6.5 with a 10% aqueous sodium carbonate solution, and then stirred for 3 hours under the same conditions.

 (3) The mixture was heated to 95 while neutralized to pH 9.5 with a 5% aqueous sodium hydroxide solution. After stirring for 12 hours under the same conditions to complete the reaction, the mixture was cooled to 50 ° C. The reaction solution (270 parts) was neutralized to pH 7.0 with 35% hydrochloric acid, and then sodium chloride (67.5 parts) was added to precipitate crystals, followed by filtration. The crystals were washed with a 20% aqueous sodium chloride solution and dried to obtain 46.9 parts of Compound No. 19 (maximum absorption wavelength in water = 420 nm). Reference Example 2 (Synthesis of Compound No. 20)

 (1) In 25 parts of ice water, 9.225 parts (0.05 mol) of cyanuric chloride was added, and the mixture was stirred and dispersed at 5 ° C or lower for 1 hour. Dissolve 9.25 parts of 2,4-diaminobenzenesulfonic acid in 70 parts of water with weak acidity, and add ice to the above dispersion, and take 1 hour at 5 ° C or less. And dropped. Further, an aqueous solution of 10% sodium carbonate was added dropwise at 5 ° C. or lower over 1 hour while adding ice, and the mixture was neutralized to pH 6.0. After reacting for 1 hour under the same conditions, 3.6 parts of sodium nitrite was added to 5 parts of water and dissolved, and then 12 parts of 35% hydrochloric acid was added all at once so that the liquid temperature did not exceed 5 ° C. Was. The mixture was stirred at 5 ° C. or lower for 1 hour to obtain 200 parts of a diazo liquid.

(2) A solution prepared by dissolving 1.45 parts of 1-ethyl-3-sulfomethyl-6-hydroxy-4-methyl-2-pyridone in 100 parts of water is added to the diazo solution of (1) while adding ice to the solution. Added below 0 ° C. Subsequently, a 10% aqueous sodium carbonate solution was added dropwise over 1 hour to neutralize to pH 7.0. The reaction was completed by stirring for 2 hours.

(3) To the reaction solution of (2), 8.40 parts of p-aminobenzenesulfonic acid was added, and the mixture was heated to 50 ° C while neutralized to pH 7.0 with a 10% aqueous sodium carbonate solution. After stirring under the same conditions for 3 hours, add 7.8 parts of diethanolamine, and add 5% water. The mixture was heated to 95 ° C. while neutralizing to pH 9.0 with an aqueous sodium oxide solution. After stirring for 6 hours under the same conditions to complete the reaction, the mixture was cooled to 50C. After neutralizing 400 parts of the reaction solution to 117.0 with 35% hydrochloric acid, 100 parts of sodium chloride was added to precipitate crystals, which were filtered. The crystals were washed with a 20% aqueous sodium chloride solution and dried to obtain 33.5 parts of a compound No. 20 (maximum absorption wavelength in water = 423 nm). Reference Example 3 (Synthesis of Compound No. 21)

 (1) Dissolve 27.5 parts of mono-sodium 2-amino-1,4-disulfonic acid salt in 150 parts of water with weak alkalinity, then add sodium nitrite 7.

The solution obtained by adding 5 parts and dissolving the mixture is added to 220% of 5% hydrochloric acid aqueous solution cooled to 5 ° C while adding ice at 5 ° C or less, and stirred for 1 hour to obtain 450 parts of diazo liquid. Was.

 (2) 1-Ethyl-3-6-hydroxy-4-methyl-2-pyridone (20.6 parts) was dissolved in water (420 parts) with a weak force, and then cooled to 10 ° C. with ice. A 10% aqueous solution of sodium carbonate and 450 parts of the diazo solution of (1) were simultaneously added at pH 8 and at a liquid temperature of 10 ° C. or lower while adding ice. The reaction was completed by stirring at pH 8 and room temperature for 12 hours. The whole reaction liquid was dried to obtain 24.1 parts of Compound No. 21 (maximum absorption wavelength in water = 4 16 nm). Industrial applicability

The phthalocyanine compound for ink jet recording of the present invention is characterized by being excellent in water solubility and having good filterability on a membrane filter in the process of producing an ink composition. Further, the ink composition of the present invention using this compound does not have crystal precipitation, physical property change, color change or the like after storage for a long time, and has good storage stability. Printed matter using the ink composition of the present invention as a Dary ink for ink jet recording has an ideal green hue without selecting a media (paper, film, etc.), and has been conventionally used for ink jet recording. It is possible to reproduce green with higher clarity than to reproduce green with yellow and cyan ink, and to reproduce the hue of a color image faithfully on paper. Furthermore, the darry of the present invention When the ink composition is used together with yellow and cyan, an ink jet recording excellent in light resistance, ozone resistance and the like can be performed. Therefore, the water-soluble phthalocyanine compound for ink jet recording of the present invention is extremely useful as a dye for green ink for ink jet recording.

Claims

• The scope of the claims  1. The following formula (1) in the form of free acid (S0 ₃ H) a MePc (SO _z A) β (1) (S0 ₂ B) τ [In the formula (1), Me represents Cu, Zn or A1, and Pc represents a phthalocyanine residue. A one NH _2; single _{NHCH 2 CH 2 OH; _ N} (CH 2 CH 2 OH) 2; one NHCH ₂ CO_〇_H; single _{NHC 2 H 4 S 0 3 H} ; nitro group, a carboxyl group, a nitrile group Or a phenol residue which may be substituted with a hydroxyl group. α represents 0 to 3,] 3 represents 0 to 2, and α represents 1 to 4, and α + i6 + Τ is 4 or less. B is the free acid form of formula (2) (2)

(In the formula (2),, and R ₂ each independently represent —H, —CH ₃ , —COO H, one NH C〇CH ₃ \ logen atom or an alkoxy group having 1 to 3 carbon atoms, and R ₃ represents —CONH ₂ , one CN or one CH ₂ S 0 ₃ H, R ₄ is an alkyl group having from 4 to 4 carbon atoms, one (CH ₂ ) qCOOH, one (CH ₂ ) _q SO 3 H (q is 1, 2 or Represents 3) or a hydroxyalkyl group having 1 to 3 carbon atoms, and n represents 0 to 2. Sulfonic acid, carboxylic acid, and hydroxyl group are all represented in the form of a free acid. Represents a donazoanilino compound residue. The water-soluble phthalocyanine compound for inkjet recording represented by the formula (2) is represented by the following formula (3)

Wherein (3), R ₃ is - CONH _2, or an _{CH 2 S 0 3 H, R} 4 is an alkyl group having a carbon number of 1 to 4, n represents each 0 or 1. 2. The water-soluble phthalocyanine compound for ink jet recording according to claim 1, 3. The compound of the formula (1) is represented by the following formula (4)

[In the formula (4), Me represents Cu, and Pc represents a phthalocyanine residue. Represents 0 to 3, a represents 1 to 2, and a + a is 4 or less. R ₃ is - CONH _2, or represents an _{CH 2 S 0 3 H, R} 4 represents an alkyl group having 1-4 carbon atoms, n represents 0 or 1. The water-soluble phthalocyanine compound for ink jet recording according to claim 1, which is a compound represented by the following formula:  4. A green composition for ink jet recording, comprising the water-soluble phthalocyanine compound for ink jet recording according to any one of claims 1 to 3.  5. An ink jet recording green composition comprising a mixture of a water-soluble phthalocyanine compound for ink jet recording according to any one of claims 1 to 3 and a yellow dye. 6. The green composition for ink jet recording according to claim 5, wherein the yellow dye is a water-soluble pyridone azo compound represented by the following formula (5).

[In the formula (5), R ₂ is each independently 1 H, —CH ₃ , 1 COOH, —NHCOCH ₃ , a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R 3 is —CONH ₂ , 1 CN or — CH ₂ SO ₃ H, R ₄ is an alkyl group having 1 to 4 carbon atoms, one (CH ₂ ) qCOOH, one (CH ₂ ) _n S 0 ₃ H (q represents 1, 2 or 3) or carbon N represents 0 to 3, and C represents a hydrogen atom, a substituent or a linking group. ] 7. The green composition for ink jet recording according to claim 6, wherein the formula (5) is the following formula (6).

[In the formula (6), R ₃ represents —C〇NH ₂ , one CN or one CH ₂ SO ₃ H, R ₄ represents an alkyl group having 1 to 4 carbon atoms, one (CH ₂ ) qCOOH, − (CH ₂ ) _q SO 3 H (q represents 1, 2 or 3) or a hydroxyalkyl group having 1 to 3 carbon atoms, n represents 0 to 3, C represents an amino group, an acetylamino group, -S 02 H, Or a group represented by the following formula (7), (8) or (9) as SO ₃ H or a free acid]

(In the formulas (7), (8) and (9), X and Y each independently represent a chlorine atom, a substituted or unsubstituted amino group or a substituted or unsubstituted hydroxyl group. D! And D ₂ are each independently one Η to one CH _3, one C_〇_〇_H, one NHCOCH _3, a halogen atom or a C 1 one 3 alkoxy group having a carbon, D ₃ one C ONH _2, one CN or - a CH ₂ S 0 ₃ H , D ₄ is an alkyl group having 1 to 4 carbon atoms, 1 (CH ₂ ) _Q COOH, — (CH ₂ ) _NS 03 H (Q represents 1, 2 or 3), or hydroxyalkyl having 1 to 3 carbon atoms And n represents 0 to 3, respectively.) 8. As the dye component, the water-soluble phthalocyanine compound for ink jet recording according to any one of claims 1 to 3 or the ink jet according to any one of claims 5 to Ί. Aqueous green ink composition for ink jet recording, characterized by containing a recording green composition. 9. As the dye component, the water-soluble phthalocyanine compound for ink jet recording according to any one of claims 1 to 3 or the ink jet ink according to any one of claims 5 to 7 Green for recording A method for producing an aqueous green ink composition for aqueous ink jet recording, comprising dissolving the composition in an aqueous medium.  10. In an ink jet recording method in which ink droplets are ejected in accordance with a recording signal to perform recording on a recording material, the ink composition uses the aqueous green ink composition for ink jet recording described in claim 8 as the ink composition. Ink jet recording method characterized by the following:  1 1. The ink jet recording method according to claim 10, wherein the recording material is an information transmission sheet.  1 2. The ink jet recording method according to claim 1.1, wherein the information transmission sheet is a surface-treated sheet.  1 3. Colored body colored with the aqueous Darwink composition for ink jet recording according to claim 8  1 4. The colored body according to claim 13, wherein the coloring is performed by pudding 1 5. An ink jet printer loaded with a container containing the aqueous green ink composition for ink jet recording according to claim 8. 1 6. Water-soluble phthalocyanine compound represented by the following formula (10) as a free acid

(In the formula (10), P c is a phthalocyanine residue, a is 1-3, α is 1-4, α + α is 4 or less, n is 0-2, and R ₂ is independently a hydrogen atom or a COOH, R ₃ one CN, - a CH ₂ S 0 ₃ H or one CONH _2, R ₄ represents - C ₂ H ₅ or an n one C ₄ H _9, respectively) 17. The scope of claims wherein the position of each substituent in CuPc is the 4-position of each benzene nucleus (4, 4 \ 4 "or 4 '' 'position in the following formula (11)). A water-soluble phthalocyanine compound according to item 16

 18. An aqueous green ink composition for ink jet recording, comprising a water-soluble phthalocyanine compound according to claim 16 or 17 as a coloring matter component.  1 9. Green composition for inkjet recording comprising a mixture of a water-soluble phthalocyanine compound and a yellow dye according to claim 16 or 17.