CN100528968C

CN100528968C - Phthalocyanine dye and use thereof for ink-jet printing

Info

Publication number: CN100528968C
Application number: CN 200480009130
Authority: CN
Inventors: 藤井隆文; 北山弘和; 难波晋一
Original assignee: Nippon Kayaku Co Ltd
Current assignee: Nippon Kayaku Co Ltd
Priority date: 2003-03-31
Filing date: 2004-03-29
Publication date: 2009-08-19
Anticipated expiration: 2024-03-29
Also published as: CN1768116A

Abstract

The present invention relates to a phthalocyanine colorant characterized in that it has, as substituents, at least one unsubstituted sulfamoyl group and at least one substituted sulfamoyl group, the total number of these groups being 2 to 4, the substituent on the substituted sulfamoyl group has a substituted triazinyl group bonded thereto through a crosslinking group, and the unsubstituted sulfamoyl group and the substituted sulfamoyl group are bonded to the phthalocyanine ring at the beta -position. Said phthalocyanine colorant is suitable for use in an ink, especially a cyan ink, for an ink-jet printer. A printed matter obtained by printing with said ink is excellent in light fastness, ozone fastness and moisture fastness.

Description

Phthalocyanine dye and spray ink Printing purposes thereof

Technical field

The present invention relates to the manufacture method of phthalocyanine dye, printing ink, printing ink group, the ink jet recording method that uses this printing ink or printing ink group, colouring agent, phthalocyanine dye.

Background technology

In recent years as image recording material, especially for the material that forms coloured image is main flow, particularly, ink-jetting style recording materials, sensible heat transfer printing type image recording material, the recording materials that use the electrofax mode, transfer-type halogenization silver sensitive materials, printing-ink, stylus etc. are widely used.In addition, in the LCD or PDP of indicating meter, in the electronic components such as the CCD of photographic equipment, use colour filter.In these coloured image recording materials or colour filter, in order to reproduce or to write down full-colour image, use the 3 primary colors pigments (dyestuff or pigment) of so-called addition colour mixture method or subtractive colour mixture method, but present situation is the pigment that does not have the absorption characteristic in the color reproduction territory of can realizing ideal and tolerate various working conditionss, and strong expectation can be improved.

Ink jet recording method is because materials cost is cheap, but fast recording, and noise is few and colored record is easy during record, so popularize fast and sustainable development.Ink jet recording method have continuously with the continuous mode of droplet jet and correspondence image information signal with droplet jet with need (on demand) mode, its discharge mode has: the mode by piezoelectric device is exerted pressure drop is discharged makes the mode that produces bubble in printing ink drop is discharged, the mode of using supersonic mode or by static the drop absorption being discharged by heat.The example that is fit to the printing ink of ink-vapor recording can be enumerated as water color ink, oil-based ink or solid (fusion) printing ink etc.

For employed pigment in the printing ink that is fit to such ink-vapor recording, requirement is good for the solvability or the dispersiveness of solvent, but high density record, tone is good, and is strong for the reactive gas in light, heat, the environment (oxidizing gas such as NOx, ozone and SOx), to the superior durability of water or medicine, good for the fixation performance that is recorded material, be difficult for infiltration, superior as the keeping quality of printing ink, nontoxicity and cheaply buying easily again.Especially strong expectation has good cyan pool, and photostabilization (to the weather resistance of light), ozone resistance (to the weather resistance of ozone gas) and wet fastness (weather resistance under high humidity) are superior, can not cause the bronze phenomenon cyanine of (also being called the bronzeization phenomenon).The bronze phenomenon is meant owing to pigment is assembled or the surface coloring element of reason is directed at glossy paper such as absorption of inks is bad etc. becomes Metal Flake, luminous phenomenon.If cause this phenomenon, then glossiness, press quality, the equal variation of printing concentration.

The skeleton that is fit to the employed water-soluble cyanine of printing ink of ink-vapor recording is representative with phthalocyanine system or tritane.The representative phthalocyanine of being reported, utilizing by wide scope ground is the phthalocyanine derivates that pigment has following A to H to classify.

A: sun blue-86 (Direct Blue 86), sun blue-87 (Direct Blue 87), sun blue-199 (Direct Blue 199), acid blue-249 (Acid Blue 249) or Reactive blue-71 known phthalocyanines such as (Reactive Blue 71) are pigment

B: the spy opens clear 62-190273 communique (document 1), spy and opens flat 7-138511 communique (document 2), spy to open phthalocyanine that 2002-105349 communique (document 3) etc. disclosed be pigment [Cu-Pc-(SO for example ₃Na) m (SO ₂NH ₂) mixture of n:m+n=1 to 4]

C: it is pigment [Cu-Pc-(CO for example that the spy opens phthalocyanine that flat 5-171085 communique (document 4) etc. disclosed ₂H) m (CONR ₁R ₂) number of n:m+n=0 to 4]

D: it is pigment [Cu-Pc-(SO for example that the spy opens phthalocyanine that flat 10-140063 communique (document 5) etc. disclosed ₃H) m (SO ₂NR ₁R ₂) number and m ≠ 0 of n:m+n=0 to 4]

E: the phthalocyanine that the special flat 11-515048 communique of table (document 6) etc. is disclosed is pigment [Cu-Pc-(SO for example ₃H) l (SO ₂NH ₂) m (SO ₂NR ₁R ₂) number of n:l+m+n=0 to 4]

F: it is pigment [Cu-Pc-(SO for example that the spy opens phthalocyanine that clear 59-22967 communique (document 7) etc. disclosed ₂NR ₁R ₂) number of n:n=1 to 5]

G: the spy opens 2000-303009 communique (document 8) and spy, and to open the phthalocyanine that 2002-249677 communique (document 9) etc. disclosed be pigment [phthalocyanine compound, the β-position of control substituting group the position of substitution gone up and imported substituent phthalocyanine is pigment: about β-position, please refer to aftermentioned explanation]

H: it is pigment that the spy opens the phthalocyanine with pyridine ring that 2003-34758 communique (document 10) etc. disclosed

Now the phthalocyanine of general widely used sun blue 86 or sun blue 199 representatives is that pigment has than the fuchsin pigment known to general or the superior feature of photostabilization of xanthein.Phthalocyanine is that pigment is with green tone under acidic conditions, not too is suitable as cyan ink.Preferably to alkaline condition, use when therefore using these pigments in neutrality as cyan ink.But, even printing ink is neutral to alkalescence, and use when being recorded material as acidic paper, then the color and luster of print may produce big variation.

Especially, even recent oxidizing gas such as nitrogen oxide gas of often adopting because of environmental problem or ozone also can cause the green and decolouring of variable color band, print concentration simultaneously and also reduce.

On the other hand, though good for tritane system color and luster, photostabilization, ozone resistance and wet fastness are very inferior.

From now on, because the use field enlarges, if be widely used in display materials such as advertisement, the situation that then is exposed to the reactive gas in light or the environment increases, so more and more expect to have the superior and cheap pigment and the printing ink of patience of good colour, photostabilization and the reactive gas (oxidizing gas such as NOx, ozone and SOx) in environment.But but be difficult to develop the cyanine (for example phthalocyanine is a pigment) and the cyan ink that can satisfy these requirements with high level.So far, the phthalocyanine of giving reactive gas patience is that pigment is disclosed in above-mentioned document 3,8 to 10 and spy and opens in the 2002-80762 communique (document 11) etc., but still can't obtain to satisfy all qualities and the cyanine that can cheaply make and cyan inks such as color and luster, photostabilization, ozone resistance and wet fastness.Thereby can't fully satisfy the demand in market.

The present invention to be solving above-mentioned problem in the past, and to reach following purpose be problem.That is, the purpose of this invention is to provide and have good colour, and the novel phthalocyanine dye of tool excellent in resistance photosensitiveness, ozone resistance and wet fastness is as cyan ink, and printing ink and the ink jet recording method that is suitable for using this phthalocyanine dye ink-jet is provided.

Summary of the invention

The inventor etc. can solve above-mentioned problem, thereby finish the present invention studying to find with specific phthalocyanine to be that the pigment that pigment is used as printing ink uses when the high phthalocyanine of good colour, photostabilization and ozone resistance is pigment in great detail.In detail; the present invention relates on specific the position of substitution (β position :), to have the sulfamyl that replaces with the substituting group that contains triazine ring and the metal phthalocyanine pigment shown in both following formulas (1) of unsubstituted sulfamyl with reference to aftermentioned; find that this pigment has good color and lusters such as cyan; photostabilization (to the weather resistance of light), wet fastness (weather resistance under high humidity) be superior, can not cause the bronze phenomenon character of (also be called and make the bronzeization phenomenon); ozone resistance (for the weather resistance of ozone gas) is also superior simultaneously, thereby finishes the present invention.Below the present invention is disclosed in detail in addition.

That is, the present invention relates to

1. the phthalocyanine dye of formula (1) expression,

{ in the formula (1), M is hydrogen atom, atoms metal, metal oxide, metal hydroxides or metal halide; R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄, R ₁₅Independent separately is replacement sulfamyl or the hydrogen atom shown in the not replacement sulfamyl shown in the formula (2), the formula (3); Wherein, R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄, R ₁₅In have 1 at least for not replacing sulfamyl, have at least 1 to be the replacement sulfamyl shown in the formula (3); R ₁, R ₄, R ₅, R ₈, R ₉, R ₁₂, R ₁₃, R ₁₆Be hydrogen atom; Do not replace the sulphonamide radix with replace the sulphonamide radix and be 2 to 4 and not replace the sulphonamide radix be 1 to 3, replace the sulphonamide radix and be 1 to 3}

-SO ₂NH ₂ (2)

In the formula (3), R ₁₇And R ₁₈Independent separately is hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic or replacement or unsubstituted thiazolinyl; A is a crosslinking group, the R of adjacency ₁₇, R ₁₈, can link mutually between the A and form ring; Y and Z independently are halogen atom separately, hydroxyl, sulfonic group, carboxyl, amino, replace or unsubstituted alkoxyl group, replace or unsubstituted cycloalkyloxy, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkene oxygen base, replace or unsubstituted alkylamino radical, replace or unsubstituted cycloalkanes amido, replace or unsubstituted aryl amine, replace or unsubstituted heterocycle amido, replace or unsubstituted enamine base, replace or unsubstituted di alkylamino group, replace or unsubstituted alkylthio, replace or unsubstituted arylthio, replace or unsubstituted heterocycle sulfenyl, replace or unsubstituted alkenylthio group; Wherein, has 1 among Y, the Z at least for having ionic wetting ability base } as substituent base

2. as the 1st phthalocyanine dye, it is formula (4) expression of Cu by M in formula (1) of the 1st,

(R in the formula ₁To R ₁₆With synonym shown in the formula (1))

3. as the 1st or the 2nd 's phthalocyanine dye, wherein, crosslinking group A is alkylidene group, cycloalkylidene or arylidene.

4. each phthalocyanine dye as in the 1st to the 3rd, wherein, at R ₂With R ₃, R ₆With R ₇, R ₁₀With R ₁₁, R ₁₄With R ₁₅Each combination in, a side separately be a hydrogen atom, the opposing party is the not replacement sulfamyl represented of formula (2), replacement sulfamyl or the hydrogen atom that formula (3) is represented, and R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄, R ₁₅In have 1 at least for not replacing sulfamyl, have 1 replacement sulfamyl at least for formula (3) expression.

5. as the 1st or the 2nd 's phthalocyanine dye, wherein, the replacement sulfamyl of formula (3) is the base shown in the following formula (5).

{ in the formula (5), B is alkylidene group, arylidene or xylylene; D and E independently are the chlorine atom separately, hydroxyl, sulfonic group, carboxyl, amino, alkoxyl group (can be by being selected from by sulfonic group, carboxyl, hydroxyl, di alkylamino group, aryl amine, acetamido, alkoxyl group, aryl, cyano group, substituting group in the group that halogen atom is formed replaces), phenoxy group (can be by being selected from by sulfonic group, carboxyl, urea groups, alkyl, substituting group more than a kind or 2 kinds in the group that alkoxyl group is formed replaces), naphthyloxy (can be by being selected from by sulfonic group, substituting group more than a kind or 2 kinds in the group that acetamido is formed replaces), benzyloxy (can replace) by sulfonic group, benzene oxyethyl group (can replace) by sulfonic group, alkylamino radical (can be by being selected from by sulfonic group, carboxyl, hydroxyl, alkoxyl group, di alkylamino group, aryl amine, aryl, halogen atom, substituting group in the group that cyano group is formed replaces), anilino (can be by being selected from by sulfonic group, carboxyl, hydroxyl, di alkylamino group, aryl amine, acetamido, urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, substituting group more than a kind or 2 kinds in the group that halogen atom is formed replaces), naphthylamine base (can replace) by sulfonic group or hydroxyl, benzamido group (can replace) by sulfonic group, phenylethylamine base (can replace) by sulfonic group, alkylthio (can be by sulfonic group, carboxyl, hydroxyl replaces) or arylthio (can be by being selected from by sulfonic group, carboxyl, hydroxyl, substituting group more than a kind or 2 kinds in the group that alkyl is formed replaces), D, have 1 among the E at least and have the ionic wetting ability base that is selected from the group of forming by sulfonic group and carboxyl } as substituting group

6. as the 1st phthalocyanine dye, wherein, either party of Y and Z be amino or replacement or unsubstituted alkylamino radical, and the opposing party is halogen atom and hydroxyl base in addition.

7. as the 6th phthalocyanine dye, wherein, the base beyond halogen atom and the hydroxyl is the aryl amine that is replaced by sulfonic group.

8. as the 1st phthalocyanine dye, wherein, the pigment content of formula (1) is all with respect to pigment, is at least more than 60%.

9. as the 1st to the 8th phthalocyanine dye, wherein, formula (1) is by making the phthalocyanine dye shown in chlorizating agent and the formula (6) or its reactant salt, sulfonic group being converted to the chlorsulfonic acid base, react with organic amine shown in the following formula (X) and amidating agent then and obtain

{ in the formula (6), M is hydrogen atom, metallic element, metal oxide, metal hydroxides or metal halide, and L is the ion or the ammonium ion of proton, alkalimetal ion, alkaline-earth metal ions, organic amine.A, b, c, d are 0 or 1, itself and be 2 to 4 integer

(in the formula (X), R ₁₇And R ₁₈Independent separately is hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic or replacement or unsubstituted thiazolinyl, and A is a crosslinking group, the R of adjacency ₁₇, R ₁₈, can link mutually between the A and form ring; Y and Z independently are halogen atom separately, hydroxyl, sulfonic group, carboxyl, amino, replace or unsubstituted alkoxyl group, replace or unsubstituted cycloalkyloxy, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkene oxygen base, replace or unsubstituted alkylamino radical, replace or unsubstituted cycloalkanes amido, replace or unsubstituted aryl amine, replace or unsubstituted heterocycle amido, replace or unsubstituted enamine base, replace or unsubstituted di alkylamino group, replace or unsubstituted alkylthio, replace or unsubstituted arylthio, replace or unsubstituted heterocycle sulfenyl or replacement or unsubstituted alkenylthio group, wherein, Y, has 1 among the Z at least for having ionic wetting ability base as substituent base.)

10. phthalocyanine dye, by making between the 4-sulfo group phthalic acid derivative or 4-sulfo group phthalic acid derivative and phthalic acid (acid anhydride) derivative react in the presence of metallic compound, obtain the sulfo metal phthalocyanines compound, make itself and chlorination reaction that sulfonic group is converted to the chlorsulfonic acid base, then, react with the organic amine shown in amidating agent and the following formula (X) and obtain phthalocyanine dye.

In the formula (X), R ₁₇, R ₁₈, A, Y, Z and above-mentioned synonym

11. as the 10th phthalocyanine dye, wherein, crosslinking group A is alkylidene group, cycloalkylidene, arylidene.

12. as the 10th or the 11st 's phthalocyanine dye, wherein, the represented organic amine of formula (X) is following formula (X '),

{ in the formula (X '), B is alkylidene group, arylidene or xylylene; D and E independently are the chlorine atom separately, hydroxyl, sulfonic group, carboxyl, amino, alkoxyl group (can be by being selected from by sulfonic group, carboxyl, hydroxyl, di alkylamino group, aryl amine, acetamido, alkoxyl group, aryl, cyano group, substituting group in the group that halogen atom is formed replaces), phenoxy group (can be by being selected from by sulfonic group, carboxyl, urea groups, alkyl, substituting group more than a kind or 2 kinds in the group that alkoxyl group is formed replaces), naphthyloxy (can be by being selected from by sulfonic group, substituting group more than a kind or 2 kinds in the group that acetamido is formed replaces), benzyloxy (can replace) by sulfonic group, benzene oxyethyl group (can replace) by sulfonic group, alkylamino radical (can be by being selected from by sulfonic group, carboxyl, hydroxyl, alkoxyl group, di alkylamino group, aryl amine, aryl, halogen atom, substituting group in the group that cyano group is formed replaces), anilino (can be by being selected from by sulfonic group, carboxyl, hydroxyl, di alkylamino group, aryl amine, acetamido, urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, substituting group more than a kind or 2 kinds in the group that halogen atom is formed replaces), naphthylamine base (can replace) by sulfonic group or hydroxyl, benzamido group (can replace) by sulfonic group, phenylethylamine base (can replace) by sulfonic group, alkylthio (can be by sulfonic group, carboxyl, hydroxyl replaces) or arylthio (can be by being selected from by sulfonic group, carboxyl, hydroxyl, substituting group more than a kind or 2 kinds in the group that alkyl is formed replaces), D, has 1 among the E at least for having the ionic wetting ability base that is selected from the group of forming by sulfonic group and carboxyl as substituent base.}

13. as each phthalocyanine dye in the 10th to the 12nd, wherein, metallic compound is a copper compound.

14. printing ink is characterized in that, the phthalocyanine dye that contains in the 1st to the 13rd each is as pigment composition.

15. as the 14th printing ink, it contains organic solvent.

16. as the 14th to the 15th printing ink, it is used for ink-vapor recording.

17. the printing ink group is characterized in that, in using the different ink-jet printer of cyan ink more than 2 kinds of pigment concentration, and each printing ink in the 14th to the 16th of at least a use.

18. ink jet recording method is discharged ink droplet being recorded the enterprising line item of material according to recording signal, it is characterized in that, use in the 14th to the 17th each printing ink or the printing ink group as printing ink.

19. the ink jet recording method as the 18th wherein, is recorded material and is information transmission sheet material.

20. as the 19th ink jet recording method, wherein, information transmission sheet material is surface treated sheet material, for have the sheet material of the ink-receiver layer that contains the white inorganic pigment particle on support.

21. container contains in the 14th to the 17th each printing ink or printing ink group.

22. ink-jet printer has the 21st container.

23. colouring agent is painted by each printing ink or printing ink group in the 14th to the 17th.

24. the manufacture method of phthalocyanine dye, it is characterized in that, 4-sulfo group phthalic acid derivative or 4-sulfo group phthalic acid derivative and phthalic acid (acid anhydride) derivative are reacted in the presence of copper compound, the compound or its salt and the chlorizating agent that obtain are reacted, after the sulfonic group chlorsulfonic acidization, react with organic amine shown in the above-mentioned formula (X) and amidating agent and obtain.

25. phthalocyanine dye, in the phthalocyanine dye shown in the following formula (14), it is more than 60% that the β position replaces body, and it is below 40% that the α position replaces body,

{ in the formula, M is hydrogen atom, atoms metal, metal oxide, metal hydroxides or metal halide, and l is less than 1 and comprise 0, and n is more than 0.3 below 3, and m is more than 1 below 3.7, and the summation of l, m, n is more than 2 below 4; R ₁₇And R ₁₈Independent of separately hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic, replacement or unsubstituted thiazolinyl A are crosslinking group, the R of adjacency ₁₇, R ₁₈Can link formation ring Y and Z between the A mutually and independently be halogen atom separately, hydroxyl, sulfonic group, carboxyl, amino, replace or unsubstituted alkoxyl group, replace or unsubstituted cycloalkyloxy, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted alkene oxygen base, replace or unsubstituted alkylamino radical, replace or unsubstituted cycloalkanes amido, replace or unsubstituted aryl amine, replace or unsubstituted heterocycle amido, replace or unsubstituted enamine base, replace or unsubstituted di alkylamino group, replace or unsubstituted alkylthio, replace or unsubstituted arylthio, replace or unsubstituted heterocycle sulfenyl or replacement or unsubstituted alkenylthio group, wherein, Y, has 1 among the Z at least for having ionic wetting ability base } as substituent base

26. as the 25th phthalocyanine dye, wherein, either party of Y and Z be amido or replacement or unsubstituted alkylamino radical, the opposing party is halogen atom and hydroxyl base in addition.

27. as the 26th phthalocyanine dye, wherein, the base beyond halogen atom and the hydroxyl is the aryl amine that is replaced by sulfonic group.

28. as the 25th phthalocyanine dye, wherein, M is a copper atom, A is the divalent crosslinking group of carbonatoms 1 to 6, l is less than 1 and comprise 0, n is more than 0.3 below 3, m is more than 1 below 3.7, the summation of l, m, n is 2 to 4, R ₁₇And R ₁₈Be hydrogen atom, Y and Z independently are amino, replacement or unsubstituted alkylamino radical, replacement or unsubstituted aryl amine, replacement or unsubstituted di alkylamino group separately, wherein, have 1 among Y, the Z at least for having ionic wetting ability base as substituent base.

Embodiment

Below, describe the present invention in detail.

Pigment shown in the above-mentioned formula of the present invention (1) is by reacting 4-sulfo group phthalic acid derivative or 4-sulfo group phthalic acid derivative and phthalic acid (acid anhydride) derivative in the presence of metallic compound; chlorizating agent and the compound that obtains are reacted; sulfonic group is converted to the chlorsulfonic acid base; react with amidating agent and specific organic amine then, import at specific the position of substitution (β position) of phthalocyanine ring and do not replace sulfamyl and replace sulfamyl and obtain.Use the print of this pigment then ozone gas to be had extremely superior patience.

Generally, though phthalocyanine derivates contains substituent R in the following formula (1) sometimes when it is synthetic unavoidablely ₁To R ₁₆The position of substitution isomer, yet these the position of substitution isomer do not distinguish mutually, thereby be regarded as same derivative more.

(in the formula (1), M, R ₁To R ₁₆With above-mentioned synonym)

In this manual, three for convenience that the position of substitution is different kind phthalocyanine derivates such as following defining classification be (1) β-position substituted type, (2) alpha-position substituted type, (3) α, β-position mixing substituted type, use when the different phthalocyanine derivates of the position of substitution is described.

In addition, in following explanation, the position of substitution of 1 to 16 is represented the substituent R of above-mentioned formula (1) ₁To R ₁₆Be combined in the position on the benzene nucleus separately, same below in this specification sheets.

(1) β-position substituted type: the phthalocyanine dye that on 2 and/or 3,6 and/or 7,10 and/or 11,14 and/or 15, has specified substituent (in this specification sheets, being sulfonic group, sulfamyl or replacement sulfamyl).

(2) alpha-position substituted type: the phthalocyanine dye that on 1 and/or 4,5 and/or 8,9 and/or 12,13 and/or 16, has specified substituent.

(3) substituted type is mixed in α, β-position: the phthalocyanine dye that has specified substituent in 1 to 16 the optional position.

Phthalocyanine dye system shown in the formula of the present invention (1) belongs to above-mentioned β-position substituted type.In addition, in the substituted phthalocyanine pigment, it is that any one of substituted type mixed in β-position substituted type, alpha-position substituted type or α, β-position, via manufacture method of the present invention the time, can from the benzene feedstock dicarboxylic acid derivatives, predict (in this phthalocyanine dye, having substituting group) in substituent position in correspondence position.If not the time, then available nitric acid etc. is decomposed into the phthalic acid derivative with this phthalocyanine dye, available NMR investigation, confirms the position of substitution at this derivative.

In the above-mentioned formula (1), M is hydrogen atom, atoms metal or its oxide compound, oxyhydroxide or halogenide.The object lesson of atoms metal can be enumerated as lithium, sodium, potassium, magnesium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, mercury, aluminium, gallium, indium, silicon, germanium, tin, lead, antimony, bismuth etc.Metal oxide can be enumerated as VO, GeO etc.Metal hydroxides can be enumerated as Si (OH) ₂, Cr (OH) ₂, Sn (OH) ₂, AlOH etc.Metal halide can be enumerated as SiCl ₂, VCl, VCl ₂, VOCl, FeCl, GaCl, ZrCl, AlCl etc.Wherein preferred Cu, Ni, Zn, Al, AlOH, most preferably Cu.

If do not limit especially,, be not particularly limited in this specification sheets as long as then the carbonatoms of alkyl, alkoxyl group, thiazolinyl, cycloalkyl and alkylidene group etc. can reach purpose of the present invention.Usually, their carbonatoms is about 1 to about 16, and preferred about 1 to about 12, and more preferably from about 1 to about 6, and further preferred about 1 to about 4.But the carbonatoms of cycloalkyl is generally about 3 to about 12, preferred about 5 to about 8.And when they had substituting group, as long as can reach purpose of the present invention, substituent kind was not particularly limited.On these basic carbochains, preferred substituted can be enumerated as: sulfonic group and by its deutero-base (sulfamyl etc.), carboxyl and by its deutero-base (carboxylic acid ester groups etc.), phosphate and by its deutero-base (phosphate-based etc.), hydroxyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted amino, replacement or unsubstituted aryl, halogen atom, cyano group etc.

As long as aryl can reach purpose of the present invention, and without particular limitation.Be generally phenyl or naphthyl etc.Preferred substituents on the aryl can enumerate as: as the cited base of the preferred substituents on the above-mentioned carbochain and urea groups, nitro, heterocyclic radical etc.

R in above-mentioned formula (3) and the formula (X) ₁₇And R ₁₈Independent separately is hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic, replacement or unsubstituted thiazolinyl.

Above-mentioned replacement or not substituted alkyl can enumerate as the alkyl of carbonatoms 1 to 12.This substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.

Above-mentioned replacement or unsubstituted cycloalkyl can be enumerated as the cycloalkyl of carbonatoms 3 to 12, the cycloalkyl of preferred carbonatoms 5 to 8.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group on this cycloalkyl.

Above-mentioned carbonatoms by alkyl in the alkyl (aralkyl) of aryl replacement is preferably about 1 to about 12.This aralkyl can have substituting group, and substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.Aryl in above-mentioned replacement or the unsubstituted aryl can be enumerated as phenyl, naphthyl.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, halogen atom.

Those of preferred 5 yuan or the 6 yuan rings of above-mentioned replacement or unsubstituted heterocyclic, their rings that can further contract.In addition, can be aromatic heterocycle, also can be non-aromatic heterocyclic.The heterocyclic example can be enumerated as pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline 99.9, quinazoline, cinnolines, phthalazines, quinoxaline, pyrroles, indoles, furans, cumarone, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, tetramethyleneimine, piperidines, piperazine, imidazolidine, thiazoline etc.In addition, these heterocycles can have substituting group, and its substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, halogen atom.

Above-mentioned replacement or unsubstituted thiazolinyl can be enumerated as the thiazolinyl of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.

A is a crosslinking group in above-mentioned formula (3) and the formula (X).Crosslinking group can be lifted usually as the hydrocarbon crosslinking group of divalent, can enumerate as the crosslinking group of carbonatoms 1 to 16, preferred carbonatoms 1 to 6.The example of this crosslinking group can enumerate as: alkylidene group, cycloalkylidene, arylidene also can be the base that these are combined to form.The example of these bases that are combined to form can be enumerated as xylylene.In addition, also can be by R ₁₇And R ₁₈The common crosslinking group that forms.Crosslinking group also can have substituting group.Substituting group can be enumerated as sulfonic group, carboxyl, hydroxyl.

Alkylidene group can be enumerated as the alkylidene group of carbonatoms 1 to 16.The part carbon atom of alkylidene group can be by nitrogen-atoms, Sauerstoffatom and sulphur atom displacement.In addition, also can be the base that alkylidene group and cycloalkylidene are combined to form.The alkylidene group of preferred carbonatoms 1 to 4.

Cycloalkylidene can be enumerated as the cycloalkylidene of carbonatoms 1 to 16.The part carbon atom of cycloalkylidene can be by nitrogen-atoms, Sauerstoffatom and sulphur atom displacement.Also can be the base that cycloalkylidene and alkylidene group are combined to form.In addition, cycloalkylidene can be crosslinked ring type hydrocarbon, also can be spiro hydrocarbon.

Arylidene can be enumerated as phenylene, naphthylidene etc.These also can have substituting group.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, halogen atom.

Y and Z independently are halogen atom separately in above-mentioned formula (3) and the formula (X), hydroxyl, sulfonic group, carboxyl, amino, replace or unsubstituted alkoxyl group, replace or unsubstituted cycloalkyloxy, replace or unsubstituted aryloxy, replace or unsubstituted heterocyclic oxy group, replace or unsubstituted aralkoxy, replace or unsubstituted alkene oxygen base, replace or unsubstituted alkylamino radical, replace or unsubstituted di alkylamino group, replace or unsubstituted aryl amine, replace or unsubstituted heterocycle amido, replace or unsubstituted aralkyl amido, replace or unsubstituted enamine base, replace or unsubstituted alkylthio, replace or unsubstituted arylthio, replace or unsubstituted heterocycle sulfenyl, replace or unsubstituted alkenylthio group Y, has 1 among the Z at least for having ionic wetting ability base as substituent base.Ionic wetting ability base is preferably the anionic hydrophilic base, can enumerate as sulfonic group, carboxyl or phosphate etc. preferred sulfonic group or carboxyl, more preferably sulfonic group.The number of ionic wetting ability base is preferably more than 2 in Y and both contained total amounts of Z, is generally 2 to 4.

These ionic wetting ability bases can be free form, also can be the ion salt or the ammonium salt of an alkali metal salt, alkaline earth salt, organic amine.Basic metal can be enumerated as sodium, potassium, lithium etc.Alkaline-earth metal can be enumerated as calcium, magnesium etc.Organic amine can be enumerated as alkylamine and alkanolamine.Alkylamine can be enumerated as the low-grade alkylamine of carbonatomss such as methylamine, ethamine 1 to 4.Alkanolamine can be enumerated as one, two or three (low-grade alkane alcohol of carbonatoms 1 to 4) amine such as monoethanolamine, diethanolamine, trolamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamines.Preferred salt is the salt of ammonium, sodium, potassium, lithium, monoethanolamine, diethanolamine, trolamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine.Be generally an alkali metal salt of sodium or lithium etc.

Y and Z are independent separately, preferably replace or unsubstituted amino, and the amino as replacing preferably can have substituent aryl amine and maybe can have substituent (C1 to C6) alkylamino radical.Can have substituent aryl amine preferably by the anilino of ionic wetting ability base replacement or the naphthylamine base that replaces by ionic wetting ability base.Can have (C1 to C6) alkylamino radical that substituent (C1 to C6) alkylamino radical is preferably replaced by ionic wetting ability base.This alkylamino radical can be any of list or di alkylamino group, but preferred single alkylamino radical.Either party of preferred Y and Z combination be (C1 to C6) alkylamino radical amino or that replaced by ionic wetting ability base, and the opposing party be by the anilino of ionic wetting ability base replacement or by the naphthylamine base of ionic wetting ability base replacement.The preferred sulfonic group of ionic wetting ability base or carboxyl, more preferably sulfonic group.

Above-mentioned replacement or unsubstituted alkoxyl group can be enumerated as the alkoxyl group of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted cycloalkyloxy can be enumerated as the cycloalkyloxy of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted aryloxy can be enumerated as phenoxy group, naphthyloxy.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, halogen atom.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Those of above-mentioned replacement or preferred 5 yuan or the 6 yuan rings of unsubstituted heterocyclic oxy group, these rings that can further contract.In addition, can be aromatic heterocycle, also can be non-aromatic heterocyclic.The heterocyclic example can be enumerated as pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline 99.9, quinazoline, cinnolines, phthalazines, quinoxaline, pyrroles, indoles, furans, cumarone, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, tetramethyleneimine, piperidines, piperazine, imidazolidine, thiazoline etc.In addition, these heterocycles can have substituting group, and its substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, halogen atom.

Above-mentioned replacement or unsubstituted aralkoxy can be enumerated as the aralkoxy of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, halogen atom.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted alkene oxygen base can be enumerated as the alkene oxygen base of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted alkylamino radical can be enumerated as the alkylamino radical of carbonatoms 1 to 12.Substituent example can be enumerated as sulfonic group, carboxyl or phosphate isoiony wetting ability base, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted cycloalkanes amido can be enumerated as the cycloalkanes amido of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted aryl amine can be enumerated as anilino, naphthylamine base.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, halogen atom.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Those of above-mentioned replacement or preferred 5 yuan or the 6 yuan rings of unsubstituted heterocycle amido, these rings that can further contract.In addition, can be aromatic heterocycle, also can be non-aromatic heterocyclic.The heterocyclic example can be enumerated as pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline 99.9, quinazoline, cinnolines, phthalazines, quinoxaline, pyrroles, indoles, furans, cumarone, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, tetramethyleneimine, piperidines, piperazine, imidazolidine, thiazoline etc.In addition, these heterocycles can have substituting group, and its substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, halogen atom.

Above-mentioned replacement or unsubstituted aralkyl amido can be enumerated as the aralkyl amido of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, halogen atom.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted enamine base can be enumerated as the enamine base of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted alkylthio can be enumerated as the alkylthio of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted cycloalkylthio can be enumerated as the cycloalkylthio of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted arylthio can be enumerated as thiophenyl, naphthalene sulfenyl.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, halogen atom.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Those of above-mentioned replacement or preferred 5 yuan or the 6 yuan rings of unsubstituted heterocycle sulfenyl, these rings that can further contract.In addition, can be aromatic heterocycle, also can be non-aromatic heterocyclic.The heterocyclic example can be enumerated as pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline 99.9, quinazoline, cinnolines, phthalazines, quinoxaline, pyrroles, indoles, furans, cumarone, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, tetramethyleneimine, piperidines, piperazine, imidazolidine, thiazoline etc.In addition, these heterocycles can have substituting group, and its substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, halogen atom.

Above-mentioned replacement or unsubstituted aromatic alkylthio can be enumerated as the aromatic alkylthio of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, halogen atom.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

Above-mentioned replacement or unsubstituted alkenylthio group can be enumerated as the alkenylthio group of carbonatoms 1 to 12.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, amino (can be replaced by alkyl, aryl and ethanoyl), aryl, halogen atom, cyano group.Wherein preferred sulfonic group, carboxyl, phosphate, hydroxyl.

B is alkylidene group, arylidene or xylylene in the above-mentioned formula (5).Alkylidene group can be enumerated as the alkylidene group of carbonatoms 1 to 16, the alkylidene group of preferred carbonatoms 1 to 6, more preferably ethylidene.Arylidene can be enumerated as phenylene, naphthylidene.These also can have substituting group.Substituent example can be enumerated as: sulfonic group, carboxyl, phosphate, hydroxyl, amino (can be replaced by alkyl, aryl and ethanoyl), urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, halogen atom.

D and E independently are the chlorine atom separately in the above-mentioned formula (5), hydroxyl, amino, alkoxyl group (can be by being selected from by sulfonic group, carboxyl, phosphate, di alkylamino group, aryl amine, acetamido, alkoxyl group, aryl, cyano group, substituting group in the group that halogen atom is formed replaces), phenoxy group (can be by being selected from by sulfonic group, carboxyl, phosphate, urea groups, alkyl, substituting group more than a kind or 2 kinds in the group that alkoxyl group is formed replaces), naphthyloxy (can be by being selected from by sulfonic group, substituting group more than a kind or 2 kinds in the group that acetamido is formed replaces), benzyloxy (can replace) by sulfonic group, benzene oxyethyl group (can replace) by sulfonic group, alkylamino radical (can be by being selected from by sulfonic group, carboxyl, phosphate, hydroxyl, alkoxyl group, di alkylamino group, aryl amine, aryl, halogen atom, substituting group in the group that cyano group is formed replaces), anilino (can be by being selected from by sulfonic group, carboxyl, phosphate, hydroxyl, di alkylamino group, aryl amine, acetamido, urea groups, alkyl, alkoxyl group, nitro, cyano group, heterocyclic radical, substituting group more than a kind or 2 kinds in the group that halogen atom is formed replaces), naphthylamine base (can replace) by sulfonic group or hydroxyl, benzamido group (can replace) by sulfonic group, phenylethylamine base (can replace) by sulfonic group, alkylthio (can be by sulfonic group, carboxyl or hydroxyl replace), arylthio (can be by being selected from by sulfonic group, carboxyl, hydroxyl, substituting group more than a kind or 2 kinds in the group that alkyl is formed replaces), in addition, D, has 1 among the E at least for having ionic wetting ability base as substituent base.

D and E are preferably independent of separately replacing or unsubstituted amino, and the amino as replacing preferably can have substituent aryl amine and maybe can have substituent (C1 to C6) alkylamino radical.Can have anilino or naphthylamine base that substituent aryl amine is preferably replaced by ionic wetting ability base.Can have (C1 to C6) alkylamino radical that substituent (C1 to C6) alkylamino radical is preferably replaced by ionic wetting ability base.This alkylamino radical can be any of single alkylamino radical or di alkylamino group, but preferred single alkylamino radical.Preferred Y and Z are combined as either party (C1 to the C6) alkylamino radical that amino or ionic wetting ability base replaces of serving as reasons, and the opposing party be by the anilino of ionic wetting ability base replacement or the situation of naphthylamine base.Ionic wetting ability base is preferably sulfonic group, carboxyl or hydroxyl, more preferably sulfonic group.

When making phthalocyanine dye of the present invention, the concrete example of the metal species (M) of the metallic compound that uses and organic amine combination to shown in the table 7, is limited to following example but have more than as table 1.In addition, the organic amine in the table is represented with the form of free acid.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Phthalocyanine dye of the present invention is by making between the 4-sulfo group phthalic acid derivative or 4-sulfo group phthalic acid derivative and phthalic acid (acid anhydride) derivative react in the presence of metallic compound, chlorizating agent and the compound (β-position substituted type sulfo group phthalocyanine) that is obtained are reacted, after sulfonic group is converted to the chlorsulfonic acid base, reacts with amidating agent and organic amine and obtain.In the 4-sulfo group phthalic acid derivative as the raw material use, contain 15 impurity to about 25 quality % of having an appointment usually at 3 sulfonated derivatives, the α position of its origin replaces body and sneaks in the object phthalocyanine dye.In order more to improve effect of the present invention (especially in order to obtain the higher printing ink of ozone resistance), preferably use at 3 raw materials that the sulfonated foreign matter content is few.

In the object phthalocyanine dye, the material that the chlorsulfonic acid base section is decomposed in the reaction is sneaked in the resultant of reaction, but and harmless.The pigment that is obtained is shown in the following formula (14), and it is principal constituent that the β position replaces body, promptly should be at least more than 60%, preferred more than 70%, more preferably more than 75%.

(in the formula (14), M, R ₁₇, R ₁₈With above-mentioned synonym.L is less than 1 and comprise 0, is preferably below 0.7, and more preferably below 0.5, most preferably below 0.3, n is more than 0.3, and preferred more than 0.7 below 3, m is 1 to 3.7, and the summation of l, m, n is 2 to 4.In addition, l, m, n value are represented with the mean value in the mixture)

When making phthalocyanine dye of the present invention, the ratio (mol ratio) of the organic amine shown in amidating agent and the formula (X) preferred so that in this phthalocyanine dye the ratio of the sulfamyl of unsubstituted sulfamyl and replacement be 1: 3 to 3: 1 ratio use.When the ratio of unsubstituted sulfamyl (reactive ratio of amidating agent) is high, with the image ozone resistance height of the ink recording that contains the phthalocyanine dye that obtains to some extent, but water-soluble low, the tendency that causes bronze phenomenon is easily arranged.On the contrary, when the ratio of organic amine was high, the water-soluble height of the phthalocyanine dye that is obtained was difficult for causing bronze phenomenon, but the tendency that has ozone resistance to reduce.Therefore, as long as the kind of organic amine shown in the corresponding employed formula (X) is done suitable adjusting with the ratio of amidating agent and organic amine, select the ideal equilibrium ratio to get final product.

The manufacture method of the compound of formula of the present invention (1) is illustrated.

At first, synthesize the metal phthalocyanine sulfonic acid shown in the above-mentioned formula (6).As previously mentioned, can secondaryly give birth to alpha-position according to the source of raw material in the phthalocyanine dye of the present invention and replace body, still, in the explanation of manufacture method, use β-position of principal constituent to replace the body record.

For the metal phthalocyanine sulfonic acid shown in the synthesis type (6), for example can obtain by in the presence of catalyzer and metallic compound, 4-sulfo group phthalic acid derivative or 4-sulfo group phthalocyanine derivates and phthalic acid (acid anhydride) derivative being reacted.Can adjust the sulfonic group number by the reaction mol ratio that changes 4-sulfo group phthalic acid and phthalic acid (acid anhydride), that is adjust the number of a to d.4-sulfo group phthalic acid derivative can be enumerated as 4-sulfo group phthalic acid, 4-sulfo group phthalate anhydride, 4-sulfophthalimide, 4-sulfo group phthalonitrile, 4-or 5-sulfo group-2-cyano group benzamide and 5-sulfo group-1,3-diimino isoindoline or their salt.Wherein, usually preferred 4-sulfo group phthalic acid or its salt.But under the situation of phthalic acid, phthalic acid (acid anhydride) and Phthalimide, need to add urea.The 4-sulfo group phthalic acid derivative of the usage quantity of urea with respect to 1 mole is 5 to 100 times of molar weights.

{ in the formula (6), M, L, a, b, c, d and above-mentioned synonym }

Reaction is carried out in the presence of solvent usually, and it is more than 100 ℃ that solvent uses boiling point, more preferably the organic solvent more than 130 ℃.Can enumerate as Pentyl alcohol, n-hexyl alcohol, hexalin, 2-methyl-1-pentene alcohol, 1-enanthol, 1-octanol, 2-Ethylhexyl Alcohol, benzylalcohol, ethylene glycol, propylene glycol, trichlorobenzene, chloronaphthalene, oil of mirbane, quinoline, tetramethylene sulfone, urea etc.The usage quantity of solvent be 4-sulfo group phthalic acid derivative 1 to 100 quality doubly.

Catalyzer can enumerate as: 1,8-diazabicyclo [5,4,0]-7-undecylene, ammonium molybdate and boric acid etc.Addition is 0.001 to 1 times of mole with respect to 1 mole of 4-sulfo group phthalic acid derivative.

Metallic compound can be enumerated as the halogenide of lithium, sodium, potassium, magnesium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, mercury, aluminium, gallium, indium, silicon, germanium, tin, lead, antimony, bismuth etc., carboxylate salt, vitriol, nitrate, acetylacetonate, carbonyl compound, complex compound etc.Can enumerate as cupric chloride, cupric bromide, nickelous chloride, nickelous acetate, cobalt chloride, cobaltous acetate, acetylacetone cobalt etc.The usage quantity of metallic compound is 0.15 to 0.35 times of mole with respect to the 4-sulfo group phthalic acid derivative or the 4-sulfo group phthalic acid derivative that amount to 1 mole with (not replacing) phthalic acid derivative.

Temperature of reaction is generally 100 to 290 ℃, is preferably 130 to 270 ℃.And, though the reaction times changes because of temperature of reaction, be generally 1 to 8 hour.After finishing, reaction obtains the form of phthalocyanine sulfonic acid or its salt by filtration, saltout (or acid out), drying.In order to make free acid, for example can carry out acid out.In order to make salify, when the salt of saltouing or can not obtain by saltouing to be expected, can utilize the common salt exchange process of for example in making the product of free acid, adding the organic or inorganic salt of being expected.

In addition, M is a copper in the above-mentioned formula (6), copper phthalocyanine sulfonic acid or its salt can be synthetic with the method that patent documentation 8 is disclosed, a, b, c, d are that the compound shown in 1 can obtain the copper phthalocyanine sulfonic acid shown in the above-mentioned formula (6) by in sulfolane solvent 4-sulfo group phthalic acid (1 mole), cupric chloride (II) (0.3 mole), ammonium phosphomolybdate (0.003 mole), urea (6 moles), ammonium chloride (0.5 mole) being reacted 6 hours in 180 ℃ in the above-mentioned formula (6).Reactive kind or usage quantity and different according to 4-sulfo group phthalic acid derivative, metallic compound, solvent and catalyzer etc. is not limited to this.

Via the phthalocyanine sulfonic acid shown in the formula (6) or its salt are for example being reacted and the phthalocyanine sulfonic acid muriate shown in the acquisition formula (8) with chlorizating agent in organic solvent, sulfuric acid, oleum or the chlorsulfonic acid equal solvent.Chlorizating agent is about 1 to about 10 times for the preferred excessive use of the sulfonic group of phthalocyanine sulfonic acid or its salt with respect to this sulfonic molar ratio, and is preferred more than 1.5 times.React employed organic solvent and can enumerate as benzene, toluene, oil of mirbane, chlorobenzene, N, dinethylformamide, N,N-dimethylacetamide etc., but be not limited to this.Chlorizating agent can be enumerated as chlorsulfonic acid, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride etc., but is not limited thereto.The part of phthalocyanine dye of the present invention is generating impurity and is sneaking in the resultant of reaction also passable through chlorination on the phthalocyanine nucleus.

[in the formula, M, a, b, c, d and above-mentioned synonym]

Then, with the organic amine shown in the phthalocyanine sulfonic acid muriate that obtained, amidating agent and the corresponding following formula (X) in water solvent, by under common pH value 6 to 10, common 5 to 70 ℃ condition, carrying out common 1 to 20 hour reaction, acquisition purpose compound.The usage quantity of amidating agent and above-mentioned organic amine both add up to (mol ratio) with respect to the muriatic sulfuryl chlorio of above-mentioned phthalocyanine sulfonic acid for waiting more than the mole, about 1 to about 20 times of moles usually, preferably about 1.5 to about 5 times of moles.The ratio that the ratio of above-mentioned organic amine needs only the replacement sulfamyl of corresponding purpose compound uses.

React employed amidating agent for being used for importing-NH ₂The medicament of base can be enumerated as ammonium salts such as ammonium chloride, ammonium sulfate, urea, ammoniacal liquor, ammonia etc., but be not limited thereto.

[in the formula (X), R ₁₇, R ₁₈, A, Y, Z and above-mentioned synonym]

In addition, the phthalocyanine compound of the usage quantity of organic amine with respect to 1 mole is generally 1 times of theoretical value more than the mole.Though there is not the upper limit,, it is 10 times below the mole from economy etc.The reactivity of organic amine is not limited to this according to reaction conditions and different.

Manufacture method to the organic amine of the correspondence shown in the formula (X) is illustrated.For example will be generally 0.95 to 1.1 mole amine, alcohols or the thio-alcohol of corresponding Y and 1 mole 2,4,6-three chloro-S-triazines (cyanuryl chloride) are in water, generally in pH value 3 to 7, usually under 5 to 40 ℃, carry out common 2 to 12 hours reaction, obtain 1 time condenses.Then, will be generally amine, alcohols or the thio-alcohol of 0.95 to 1.1 mole corresponding Z,, under 5 to 80 ℃, carry out common 0.5 to 12 hour reaction usually, obtain 2 times condenses usually in pH value 4 to 10.Then, two amines of 1 to 50 mole corresponding crosslinking group usually in pH value 9 to 12 usually, under 5 to 90 ℃, are carried out common 0.5 to 8 hour reaction usually, obtain the compound of above-mentioned formula (X).In addition, the order of condensation is suitably determined in response to the reactive of all cpds, is not limited to this.

The part of phthalocyanine dye of the present invention also can form phthalocyanine ring (Pc) dipolymer (for example Pc-L-Pc) by the concatenating group (L) of divalent or dipolymer generates impurity, sneaks in the resultant of reaction, and the L of a plurality of existence this moment separately can be identical or different.

Divalent concatenating group shown in the L can be enumerated as alkylsulfonyl (SO ₂-) ,-SO ₂-NH-SO ₂-etc.In addition, this concatenating group also can be the formed base of these base combinations.

The phthalocyanine dye of the present invention that is obtained thus can be isolated by filtering etc. at acid out or after saltouing.Saltout preferably for example acid to alkalescence, preferred pH value is that 1 to 11 scope is saltoutd.Temperature when saltouing there is no special qualification, and generally at 40 to 80 ℃, preferably heating back adds salt etc. and saltouts in 50 to 70 ℃.

Obtain for form with the phthalocyanine dye shown in the above-mentioned method synthetic above-mentioned formula of the present invention (1) with free acid form or its salt.In order to make free acid, for example can carry out acid out.In order to make salify, when the salt of saltouing or can not obtain by saltouing to be expected, can utilize the common salt exchange process of for example in making the product of free acid, adding the organic or inorganic salt of being expected.

Cyan ink of the present invention contains the phthalocyanine dye of the above-mentioned formula (1) of aforesaid method manufacturing, modulates as medium with water, but when this printing ink used as ink for ink-jet recording, the preferred contained chlorion (Cl of phthalocyanine dye ^-) and sulfate radical (SO ₄ ^-2) wait anionic content few, the standard of its content is counted below the 5 quality % with the total content of chlorion and sulfate radical in phthalocyanine dye, below the preferred 3 quality %, below the 1 quality %, is below the 1 quality % in printing ink more preferably.In order to make the few phthalocyanine dye of the present invention of chlorion and sulfate radical, for example by the usual method of reverse osmosis membrane or methods such as the dry product of phthalocyanine dye of the present invention or wet cake stirring in the mixed solvent of alcohol and water, filtration, drying are carried out desalting treatment get final product.Employed alcohol is the lower alcohol of carbonatoms 1 to 4, the alcohol of preferred carbonatoms 1 to 3, more preferably methyl alcohol, ethanol or 2-propyl alcohol.When carrying out desalting treatment, can adopt the boiling point postcooling that is heated near employed alcohol, the method for carrying out desalination with alcohol.The content of chlorion and sulfate radical is measured with for example ion chromatography.

When cyan ink of the present invention is used as ink for ink-jet recording, preferably use few (except the phthalocyanine frame institute containing metals (M in the formula (1))) of metal (positively charged ion) equal size such as heavy metal (ion), calcium, silicon-dioxide such as the contained zinc of phthalocyanine dye, iron.For example in the purifying dry product of phthalocyanine dye, heavy metals such as zinc, iron (ion), calcium, silicon-dioxide etc. are below the about separately 500ppm of metal (positively charged ion) for the standard of its content.The content of heavy metal (ion) and metal (positively charged ion) is measured by ion chromatography, atom light absorption method or inductance coupled plasma (ICP:Inductively Couples Plasma) luminescence analysis.

Phthalocyanine dye 0.1 to the 8 quality % that contains above-mentioned formula (1) in the printing ink of the present invention, preferred 0.3 to 6 quality %.The printing ink of lower concentration contains phthalocyanine compound 0.1 to 2.5 quality % of the present invention.

Printing ink of the present invention can be modulated as medium by water.Mixture 0.3 to the 6 quality % that contains the compound or its salt of the above-mentioned formula (1) that possesses above-mentioned condition that obtains by aforesaid operations in the printing ink of the present invention.Printing ink of the present invention can further contain water-miscible organic solvent as required in the scope that does not influence effect of the present invention.Water-miscible organic solvent can be used as the dyestuff solvating agent, drying prevents uses such as agent (wetting agent), viscosity modifier, penetration enhancer, surface tension adjustment agent, defoamer.Other printing ink modulator can be enumerated and adjust agent, chelating reagent, rust-preventive agent, UV light absorber, viscosity modifier, dyestuff solvating agent, anti-fading agent, emulsion stabilizer, surface tension as: Antisepticize and mildew preventive, pH and adjust known additives such as agent, defoamer, dispersion agent, dispersion stabilizer.The content of water-miscible organic solvent is with respect to all use 0 to the 60 quality % of printing ink, preferred 10 to 50 quality %, and the printing ink modulator is with respect to all use 0 to the 20 quality % of printing ink, preferred 0 to 15 quality %.Remainder beyond above-mentioned is a water.

The present invention operable water-miscible organic solvent can be enumerated as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, C1 to C4 such as trimethyl carbinol alkanol, N, dinethylformamide or N, carboxylic acid amides such as N-N,N-DIMETHYLACETAMIDE, 2-Pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, 1,3-methylimidazole alkane-2-ketone or 1,3-dimethyl hexahydropyrimidine-hetero ring type ketone such as 2-ketone, acetone, methyl ethyl ketone, 2-methyl-2-hydroxyl pentane-ketone or keto-alcohols such as 4-ketone, tetrahydrofuran (THF), cyclic ethers such as dioxane, ethylene glycol, 1,2-or 1, ammediol, 1,2-or 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, Diethylene Glycol, triethylene glycol, TEG, dipropylene glycol, the sulfo-glycol ether, polyoxyethylene glycol, polypropylene glycols etc. have the monomer of (C2 to C6) alkylidene group unit, oligopolymer or poly-alkylene alcohol, thioglycol, glycerol, hexane-1,2, polyvalent alcohols (triol) such as 6-triol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, (C1 to C4) alkyl oxide of polyvalent alcohol such as triethylene glycol monomethyl ether or Triethylene glycol ethyl ether, gamma-butyrolactone or methyl-sulphoxide etc.

In printing ink of the present invention, preferred water-miscible organic solvent can enumerate as: the list of carbonatoms 3 to 8 or polyvalent alcohol and can have the 2-Pyrrolidone etc. of the alkyl substituent of carbonatoms 1 to 3, polyvalent alcohol preferably has 2 to 3 hydroxyls.Particularly be Virahol, glycerol, list, two or triethylene glycol, dipropylene glycol, 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, butanols etc., more preferably Virahol, glycerol, Diethylene Glycol, 2-Pyrrolidone.These water-miscible organic solvents can use separately, also can mix use.

Antisepticize and mildew preventive can be enumerated as: organosulfur system, organonitrogen sulphur system, organic halogen system, halogenated allyl sulfone system, iodo propargyl system, N-haloalkane sulphur system, benzothiazole system, nitrile system, pyridine system, oxine system, benzothiazole system, isothiazoline, dithiol system, pyridine-N-oxide system, nitropropane system, organotin system, phenol system, quaternary ammonium salt system, triazine system, thiadiazine system, anilide system, the Buddha's warrior attendant methane series, dithiocar-bamate (ester) is, bromination indone system, benzyl acetate bromide system, compounds such as inorganic salt system.The organic halogen based compound can be enumerated as sodium pentachlorophenol, the pyridine-N-oxide based compound can be enumerated as 2-pyridine mercaptan-1-sodium oxide, the inorganic salt based compound can be enumerated as anhydrous sodium acetate, isothiazoline be chemical combination can enumerate as: 1,2-benzisothiazole-3-ketone, 2-n-octyl-4-isothiazoline-3-ketone, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 5-chloro-2-methyl-4-isothiazoline-3-ketone magnesium chloride, 5-chloro-2-methyl-4-isothiazoline-3-ketone calcium chloride, 2-methyl-4-isothiazoline-3-ketone calcium chloride etc.Other Antisepticize and mildew preventive can be enumerated as sodium sorbate, Sodium Benzoate etc. (for example アベシア company make プロ Network セ Le GXL (S) (trade(brand)name), プロ Network セ Le XL-2 (S) (trade(brand)name) etc.).

It is purpose with the stability that improves the printing ink preservation that pH adjusts agent, all can use as long as the pH value of printing ink can be controlled at the arbitrary substance of 6.0 to 11.0 scopes.Can enumerate as alkanolamines such as diethanolamine, trolamines, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, or alkali-metal carbonate such as Quilonum Retard, yellow soda ash, salt of wormwood etc.

Chelating reagent can be enumerated as sodium ethylene diamine tetracetate, sodium nitrilo triacetate, hydroxyethylethylene diamine tri-acetic acid sodium, diethylene-triamine pentaacetic acid sodium, uramildiacetic acid sodium (sodium uramildiacetate) etc.Rust-preventive agent can be enumerated as: acid accumulator sulfite, Sulfothiorine, mercaptoethanol acid ammonium, di-isopropyl ammonium nitrite, four pentaerythritol tetranitrates, dicyclohexyl ammonium nitrite etc.

As UV light absorber, can use with for example benzophenone based compound, benzotriazole based compound, styracin based compound, triazine based compound, stilbene based compound or benzoxazole based compound as the absorption ultraviolet ray of representative and send the compound of fluorescence, also can use so-called white dyes.

Viscosity modifier can be enumerated except water-miscible organic solvent as water-soluble high-molecular compound, can enumerate as polyvinyl alcohol, derivatived cellulose, polyamine, poly-imines etc.

The dyestuff solvating agent can be enumerated as urea, ε-Ji Neixianan, ethylene carbonate etc.

Anti-fading agent is that purpose is used with the keeping quality that improves image.Anti-fading agent can use the anti-fading agent of various organic systems and metal complex system.Organic anti-fading agent can be enumerated hydroquinones, alkoxy benzene phenols, dialkoxy phenol, phenol, phenyl amines, amine, indane class, chroman class, alkoxy benzene amine, heterocyclic etc., and metal complex has nickel complex, zinc complex etc.

Surface tension adjusts agent and can enumerate as tensio-active agent, can enumerate as anion surfactant, amphoterics, cats product, nonionogenic tenside etc.Anion surfactant can be enumerated as alkyl sulfocarboxylic hydrochlorate; sulfonated; the polyethylene oxide alkyl ethers acetate; N-acylamino acid and salt thereof; the N-acyl methyl taurine salt; alkyl-sulphate polyoxy sulfated alkyl ether; alkyl-sulphate polyethylene oxide alkyl ethers phosphoric acid salt; RA rosin acid; the Viscotrol C sulfuric acid; the lauryl alcohol sulfuric acid; alkylphenol type phosphoric acid ester; alkyl type phosphoric acid ester; alkylallyl sulfonate acid; the diethyl sulfosuccinate; diethylhexyl sulfo-succinic acid dioctyl sulfosuccinate etc.Cats product can be enumerated as 2-vinylpyridine piperidine derivatives, poly 4 vinyl pyridine derivative etc.Amphoterics can be enumerated as: lauryl dimethylin acetate trimethyl-glycine, 2-alkyl-N-carboxyl methyl-N-hydroxyethyl imidazoles trimethyl-glycine, coco-nut oil fatty acid amidopropyl dimethylin acetate trimethyl-glycine, the poly-amino-ethyl glycine of poly-octyl group and other imidazolidine derivatives etc.Nonionogenic tenside can be enumerated as polyoxyethylene nonylplenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, the polyoxyethylene lauryl ether, polyethylene oxide alkyl ethers, ethers such as polyoxy allyl group alkyl oxide system, polyoxyethylene oleic acid, the polyoxyethylene oleic acid ester, the polyoxyethylene SUNSOFT Q-182S, the sorbitan laurate, sorbitan monostearate, sorbitan monooleate, Span-83, the polyoxyethylene monoleate, esters such as polyoxyethylene stearate system, 2,4,7,9-tetramethyl--5-decine-4, the 7-glycol, 3,6-dimethyl-4-octyne-3, the 6-glycol, 3, (for example day is believed サ one Off イノ one Le 104 that chemical company makes to 5-dimethyl-1-hexin-acetylene series ethylene glycol systems such as 3-alcohol, 82,465, オ Le Off イ Application STG etc.) etc.These printing ink modulators can use separately, also can mix use.In addition, the surface tension of printing ink of the present invention is generally 25 to 70mN/m, and more preferably 25 to 60mN/m.The viscosity of printing ink of the present invention is preferably below the 30mPas, more preferably is adjusted at below the 20mPas.

Can use fluorine prime system, silicone compounds as defoamer in case of necessity.

In the manufacture method of printing ink of the present invention, there is no particular restriction to each medicament dissolved order.When modulation printing ink, ion exchanged water that the preferred impurity of used water is less or distilled water etc.Also can use film filter etc. to carry out secondary filter in case of necessity, remove inclusion, the printing ink of using as ink-jet printer preferably carries out secondary filter when using.The aperture of carrying out the strainer of secondary filter is generally 1 micron to 0.1 micron, is preferably 0.8 micron to 0.2 micron.

Printing ink of the present invention not only can be used for unicolor image and forms, and also can be used for panchromatic image and forms.In order to form full-colour image, also can be used as printing ink groups such as carmetta printing ink, Yellow ink, black ink and use.In addition, in order to form higher meticulous image, also can be used as with the printing ink group of light magenta printing ink, blue ink, green ink, orange ink, deep yellow printing ink, gray ink etc. and usefulness and use.

As the pigment of Yellow ink applicatory, can use all pigments.For example can enumerate: have phenol, aphthols, phenyl amines, as aryl or the heterocyclic radical azoic dyestuff as coupling composition (hereinafter referred to as the coupler composition) such as the heterocyclic of pyrazolone or pyridone etc., open chain type activity methene compound class; Has the azomethine dyes as the coupler composition such as open chain type activity methene compound class; As methyne dyestuffs such as Ben Yajiaji dyestuff or single methyl oxonol dyestuffs; As the quinone based dye of naphthoquinone dyestuff, anthraquinone dye etc., dyestuff in addition can be enumerated as quinophthalone dyestuff, nitro nitroso-dye, acridine dye, dihydroketoacridine dyestuff etc.

As carmetta pigment applicatory, can use various pigments.Can enumerate as: have the arylazo dyestuff as the coupler composition such as phenol, aphthols, phenyl amines; Has the azomethine dyes as the coupling composition such as pyrazolone, Pyrazolotriazole class; Methyne dyestuffs such as arylidene dyestuff, styryl dye, merocyanine dyes, cyanine dyes, oxonol dyestuff; Carbonium ion dyestuffs such as diphenylmethane dye, triphenhlmethane dye, xanthene dye; Condensation polycyclic dyestuffs such as quinone dye well dioxazine dyestuff such as naphthoquinones, anthraquinone, anthrapyridone etc.

Each above-mentioned pigment also can be a chromophoric part and dissociates, present yellow, carmetta, blue pigment of all kinds at first, this moment to positively charged ion also can be inorganic cation as basic metal, ammonium, as the organic cation of pyridine, quaternary ammonium salt, more can be section construction and have these polymerizing cationically.Black pigment applicatory can be enumerated except two azos, trisazo-, Tetrakisazo dyes as the dispersion of carbon black.

Recording methods such as printing ink of the present invention can be used for printing, manifolding, marking, writes, drawing, punching press are particularly useful for ink jet printing method.

Ink jet recording method of the present invention is by to above-mentioned synthetic inking energy, be subjected to the picture material known, that is common paper, resin coated paper, ink-jet dedicated paper, glossy paper, gloss film, the shared paper of electrofax, fiber or cloth (Mierocrystalline cellulose, nylon, wool etc.), glass, metal, pottery, leather etc. are gone up and are formed image.

To give glossiness or water tolerance, improving weathering resistance is purpose when forming image, can and disperse thing (also being called polymer latex) with polymeric microsphere.Be recorded the period of giving polymer latex on the material can be before giving tinting material, afterwards or simultaneously, so can be in being recorded material when adding, can in printing ink, also can be used as the independent fraction of polymer latex and use.

Below, be illustrated for using printing ink of the present invention to carry out the employed material (especially recording paper and recording sheet) that is recorded of spray ink Printing.The support of recording paper and recording sheet can use by waste and old paper paper pulp such as mechanical pulps such as dissolving pulps such as LBKP, NBKP, GP, PGW, RMP, TMP, CTMP, CMP, CGP, DIP etc. to be formed, in case of necessity additives such as pigment, tackiness agent, cementing agent, fixing salt, cationics, paper power toughener are mixed, use the support of various devices manufacturings such as fourdrinier machine, mould machine etc.Also can be any of synthetic paper, plastic film chip beyond these supports, the thickness of preferred support is that 10 to 250 μ m, base unit weight are 10 to 250g/m ²Support can directly be arranged at ink-receiver layer and undercoat, and also available starches, polyvinyl alcohol etc. are provided with ink-receiver layer and undercoat after carrying out the gluing squeezing or the cementation coating being set.In addition, support also can carry out planarization by machine calender, TG rolling press, the isobaric optical mechanical apparatus of soft press-polishing machine.In the present invention, support more preferably uses two sides polyolefine (for example polyethylene, polystyrene, polyethylene terephthalate, polybutene and these multipolymer) laminated paper and plastics film.The preferred dyestuff (for example cobalt blue, ultramarine, Neodymium trioxide) that adds white pigment (for example titanium oxide, zinc oxide) or have tone in the polyolefine.

Ink-receiver layer set on the support also can contain pigment or aqueous binder.The pigment optimization white pigment, white pigment can be enumerated as white inorganic pigments such as: lime carbonate, kaolin, talcum, clay, diatomite, synthetic amorphous silica, pure aluminium silicate, Magnesium Silicate q-agent, Calucium Silicate powder, oxygen aluminum hydride, aluminum oxide, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulphide, zinc carbonate, pigment dyestuffs such as polystyrene pigment, acrylic acid series pigment, urea resin, melamine resin etc.The contained white pigment of ink-receiver layer is preferably porous inorganic pigment, especially synthetic amorphous silica that the pore area is big etc.Synthetic amorphous silica can use the silicic anhydride that obtained by the dry type manufacturing process and the moisture silicic acid that obtained by the wet type manufacturing process any, preferably especially uses moisture silicic acid.

The contained aqueous binder of ink-receiver layer can be enumerated as water dispersible macromolecular compounds such as water-soluble high-molecular compound, styrene butadiene latices, acrylic latex such as: polyvinyl alcohol, silanol modified polyethylene alcohol, starch, cationic starch, casein, gelatin, Walocel MT 20.000PV, Natvosol, polyvinylpyrrolidone, poly-alkylene oxygen, poly-alkylene oxygen derivatives etc.These aqueous binders can use separately, also can merge use more than 2 kinds.In the present invention, in these especially polyvinyl alcohol, silanol modified polyethylene alcohol from for the anti-separability point of the tack of pigment, ink-receiver layer, being fit to.Ink-receiver layer also can contain mordant, anti-hydrated agent, photostabilization rising agent, tensio-active agent, other additive except pigment and water-based tackiness agent.

The mordant that adds in the ink-receiver layer can use for example polymerization mordant.

Anti-hydrated agent is effective to water-fastization of image, the special preferred cationic resin of these anti-hydrated agents.These resin cation (R.C.)s can be enumerated as polymeric amide polyamine Epicholorohydrin, polymine, polyamine sulfone, dimethyl diallyl ammonium chloride polymkeric substance, cationic polyacrylamide, colloid silica etc., special preferred polyamide polyamine Epicholorohydrin in these resin cation (R.C.)s.The content of these resin cation (R.C.)s is preferably 1 to 15 quality % with respect to the total solids composition of ink-receiver layer, preferred especially 3 to 10 quality %.

The photostabilization rising agent can enumerate as: zinc sulfate, zinc oxide, hindered amine are UV light absorber such as antioxidant, benzophenone series, benzotriazole system etc.Preferably sulfuric acid zinc in these.

Tensio-active agent has as coating additive, peels off the function of modifying agent, slip modifying agent or static inhibitor.Can also use organofluorine compound substitution list surface-active agent.Organofluorine compound is preferably hydrophobic.It is tensio-active agent, oily fluorine based compound (for example fluorocarbon oil) and solid state fluorine cpd resin (for example tetrafluoroethylene resin) that the example of organofluorine compound comprises fluorine.The additive that other ink-receiver layer adds can enumerate as: pigment dispersing agent, tackifier, defoamer, dyestuff, white dyes, sanitas, pH adjust agent, matting agent, hard coat agent etc.In addition, ink-receiver layer can be 1 layer, also can be 2 layers.

Recording paper and recording sheet also can be provided with undercoat, and the addible composition of this layer can be enumerated as white pigment, aqueous binder, other composition.Undercoat contained white pigment can be enumerated as light calcium carbonate, water-ground limestone, kaolin, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, stain white, pure aluminium silicate, diatomite, Calucium Silicate powder, Magnesium Silicate q-agent, synthetic amorphous silica, colloid silica, colloidal alumina, pseudobochmite, aluminium hydroxide, aluminum oxide, lithopone, zeolite, endellite, magnesiumcarbonate, white inorganic pigments such as magnesium hydroxide, the polystyrene plastic pigment, the acrylic acid series plastic pigment, polyethylene, microcapsule, urea resin, pigment dyestuffs such as melamine resin etc.

The contained aqueous binder of undercoat can be enumerated as water dispersible polymers such as water-soluble polymer, styrene butadiene latices, vinylformic acid emulsion such as vinylbenzene/maleate copolymer, styrene/acrylic salt copolymer, polyvinyl alcohol, silanol modified polyethylene alcohol, starch, cationic starch, casein, gelatin, carboxymethyl cellulose, Natvosol, polyvinylpyrrolidone etc.Other contained composition of undercoat can be enumerated as defoamer, suds suppressor, dyestuff, white dyes, sanitas, anti-hydrated agent etc.

Also can add polymer latex in the formation layer (comprising undercoat) of ink jet recording paper and recording sheet.Polymer latex is to improve size stabilization, to prevent to crispatura, prevent to adhere, prevent that the film rerum naturas such as slight crack of film from being that purpose is used.If in containing the layer of mordant, add the polymer latex of second-order transition temperature low (below 40 ℃), can prevent that then layer from producing slight crack or crispatura.In addition, adding the high polymer latex of second-order transition temperature in undercoat also can prevent to crispatura.

These recording papers and recording sheet are commonly referred to as the ink-jet dedicated paper, glossy paper or gloss film, commercially available for example have: ピ Network トリコ (trade(brand)name: Asahi Glass (strain) is made), colored BJ paper, higher-grade Graduate paper, カラ one BJ Off オト Off イ Le system シ one ト, スパ one Off オトペ one パ one, プロ Off エ Star シヨ Na Le Off オトペ one パ one (be trade(brand)name: Canon's (strain) makes), カラ one イメ one ジジエ Star ト (trade(brand)name: Sharp's (strain) makes), PM description paper, ス one パ one Off アイ Application Graduate Zhuan Yong Guang swamp film (be trade(brand)name: Epson (strain) is made), エ Network Off アイ Application (trade(brand)name: the strain of the マ of Hitachi Network セ Le) make) etc.In addition, in the ink jet recording method that uses printing ink of the present invention, as being recorded material, recording paper and recording sheet with the ink-receiver layer that contains the white inorganic pigment particle in support play a role especially effectively.Certainly also can use common paper.

Colouring agent of the present invention is to use ink-jet printer, will be colored the painted colouring agent of material with above-mentioned printing ink.Be colored material so long as above-mentionedly be recorded material and get final product with the painted article of other ink-jet printer, and without particular limitation.

In order to be recorded the enterprising line item of material,, be recorded in to be recorded on the material with usual method and get final product as long as will contain the prescribed position that the container of for example above-mentioned printing ink is installed in ink-jet printer by ink jet recording method of the present invention.Ink-jet printer can enumerate as: utilize mechanicalness vibration the piezoelectricity mode printer or utilize the bubble of the bubble that heating generates to spray the printer of (registered trademark) mode.

Printing ink of the present invention can not precipitate in storage, separate.Also can not block injector (ink gun) when in addition, printing ink of the present invention is used for ink jet printing.Even printing ink of the present invention utilizes continuous inkjet printer under the certain recirculation of long time or utilize and intermittently use with need (on demand) formula ink-jet printer, also can not produce the variation of physical properties.

When using desirable pigment, printing ink of the present invention is the cyan of distinctness.Can obtain the superior and photostabilization of ozone resistance, record thing that water tolerance is also superior when using printing ink of the present invention.Use as deep or light cyan ink group and more can obtain ozone resistance and photostabilization, record thing that water tolerance is superior.In addition, use printing ink such as other yellow, carmetta, other in case of necessity green, redness, orange, blueness jointly, can access the tone in extensive visual field, can obtain the superior and photostabilization of ozone resistance, record thing that water tolerance is also superior.

[embodiment]

Below, by embodiment the present invention is made more specific description." part " reaches " % " unless otherwise noted herein, is quality criteria.

Embodiment 1

M is that copper, β position have 2 replacement sulfamyl that do not replace sulfamyl and 2 formulas (3) in the formula (1), and Y is 2 in the formula (3), 5-disulfobenzene amido, and Z is ethylidene, R for amino, A ¹⁷, R ¹⁸Be compound synthetic of hydrogen atom

(1) synthetic (M is a copper, and a, b, c, d are 1, and L is the compound of the formula (6) of sodium) of copper phthalocyanine tetrasulfonic acid tetra-na salt (β position substituted type)

In being furnished with the four-hole boiling flask of cooling tube, add 40 parts of tetramethylene sulfone, in 1 hour, be warming up to 180 ℃, in wherein adding 40 parts of 4-sulfo group phthalic acid list sodium salts, 4.5 parts of ammonium chlorides, 55 parts in urea, 0.5 part of ammonium molybdate, 6 parts of cupric chlorides (II), under same temperature, stirred 6 hours.After reaction solution is cooled to 40 ℃ object is filtered with the Nutsche strainer, with 400 parts methanol cleaning.Then, in the wet cake that is obtained, add 300 parts of water, the pH value is adjusted into 11, stirred 1 hour down in 80 ℃ with 48% aqueous sodium hydroxide solution.Adding 35% aqueous hydrochloric acid while stirring, to make the pH value be 3, slowly adds 80 parts in sodium-chlor.The crystallization that leaching is separated out is cleaned for 150 parts with 20% sodium chloride aqueous solution, obtains 90 parts of wet cakes.Then, add 210 parts of methyl alcohol, stirred 1 hour, the crystallization that filtering separation is separated out, with 300 parts of clean after drying of 70% methanol aqueous solution, 22.9 parts of the β position substituted type copper phthalocyanine sulfonic acid tetra-na salts of acquisition formula (6) are the cyan crystallization.λ max:629nm (in the aqueous solution).

(2) copper phthalocyanine four SULPHURYL CHLORIDE (β position substituted type) is synthetic

Below 60 ℃, slowly add 9.8 parts of copper phthalocyanine tetrasulfonic acid tetra-na salts while in 79 parts of chlorsulfonic acids, stir, reacted 4 hours in 120 ℃.Then, reaction solution is cooled to 80 ℃,, under 80 ℃, reacted 2 hours, under 90 ℃, reacted 1 hour again with dripping 47.6 parts of thionyl chlorides in 30 minutes.Reaction solution is cooled to below 30 ℃, slowly is injected in 700 parts of the frozen water, filter the crystallization of being separated out, clean for 200 parts, 35.2 parts of the wet cakes of acquisition copper phthalocyanine four SULPHURYL CHLORIDE with 2% ice-cooled aqueous hydrochloric acid.

(3) (Y is 2 to following formula (X-1) in the formula (X), and 5-disulfobenzene amido, Z are that amino, A are ethylidene, R ¹⁷, R ¹⁸Be the compound of hydrogen atom) synthetic

In 300 parts of frozen water, dropped into Lipar OH2.9 branch, cyanuryl chloride 96.5 minutes, stirred 30 minutes.Then drop into aniline-2,150.8 parts of 5-disulfonate sodiums (purity 91.2%), to keep the pH value be 2.7 to 3.0 to react 2 hours under 10 to 15 ℃ while add 25% aqueous sodium hydroxide solution, reacted 2 hours under in 25 to 30 ℃.Then, be cooled to reaction solution below 10 ℃ after, add 25% aqueous sodium hydroxide solution, the pH value is adjusted into 10.0.In this reaction solution, add 60.7 parts of 28% ammoniacal liquor, reacted 2 hours under in 10 to 15 ℃, reacted 2 hours under in 27 to 30 ℃ again.Then, drop into 600 parts of quadrols, under 80 ℃, reacted 1 hour.Liquid measure is adjusted into 2000 parts, drops into 200 parts in sodium-chlor, the concentrated hydrochloric acid that drips is adjusted into 1.0 with the pH value, and crystallization is separated out, and the crystallization that filtering separation is separated out is cleaned for 500 parts with 20% sodium chloride aqueous solution, obtains 245.9 parts of wet cakes.245.9 parts of the wet cakes that obtained are dropped in 1700 parts of the methyl alcohol, add 90 parts of entry, stir down in 60 ℃ and made its suspension after-filtration in 1 hour, with methanol cleaning, drying, 125.8 parts of the compounds of acquisition formula (X-1).

(4) purpose compound (the β position replaces body) is synthetic

35.2 parts of copper phthalocyanine four SULPHURYL CHLORIDE wet cakes that (2) are obtained drop in 200 parts of the frozen water, stir and make suspension.Maintain after 10 minutes and splash into 28% ammoniacal liquor below 5 ℃, adjusting the pH value is 9.0.Then, in this suspension, inject 2 parts of ammoniacal liquor and 8.5 parts of water-soluble aqueous solution of 100 parts of formula (X-1) compound, the pH value is maintained 9.0, under 10 ℃, reacted 2 hours while add 28% ammoniacal liquor, under 20 ℃, reacted 2 hours, under 50 ℃, reacted 1 hour.Add entry, liquid measure is adjusted into 500 parts, drop into 100 parts in sodium-chlor, crystallization is separated out, the crystallization that filtering separation is separated out is cleaned for 200 parts with 20% sodium chloride aqueous solution, obtains 41.0 parts of wet cakes.Water-soluble once more, total amount is adjusted into 400 parts, add 80 parts in sodium-chlor after being warming up to 60 ℃, add 35% aqueous hydrochloric acid the pH value is adjusted into 1.0, separate out crystallization.The crystallization that filtering separation is separated out is cleaned for 200 parts with 20% sodium chloride aqueous solution, obtains 51.5 parts of wet cakes.51.5 parts of the wet cakes that obtained are dropped in 500 parts of the methyl alcohol, stir down in 60 ℃ and made its suspension after-filtration in 1 hour,, obtain 8.9 parts of blue crystallizations with methanol cleaning, drying.The λ max of this compound is 608.5nm (in the aqueous solution).

It is more than 75% that the β position of this compound replaces body, if infer from the input amount of reaction and formula (X-1) compound, for the m in the formula (9) (the position of substitution does not have appointment, represents with free acid form) is 2, n is 2 compound.But the result with the analysis of liquid chromatography mass analyzer also confirms to have sulfonic group.The analytical results that merges other infers that l value (sulfonic group) is about 0.3, the scope of n value (replacement sulfamyl) 0.5 to 2, thus inference all the other be m (not replacing sulfamyl), the summation of l, m and n is 4, near actual value.

Embodiment 2

Similarly to Example 1 phthalocyanine dye synthetic of formula (1) except in the pigment of the foregoing description 1, the β bit substituent being changed to 3 replacement sulfamyl that do not replace sulfamyl and 1 formula (3)

In 100 parts of frozen water, drop into 17.6 parts of the copper phthalocyanine four SULPHURYL CHLORIDE wet cakes that embodiment 1 (2) obtained, stir and make its suspension.Be maintained at after 10 minutes and splash into 28% ammoniacal liquor below 5 ℃, the pH value is adjusted into 9.0.Then, in above-mentioned suspension, inject 0.5 part of ammoniacal liquor and 2.1 parts of water-soluble aqueous solution of 30 parts of formula (X-1) compound, the pH value is maintained 9.0, under 10 ℃, reacted 2 hours while add 28% ammoniacal liquor, under 20 ℃, reacted 2 hours, under 50 ℃, reacted 1 hour.Add entry, liquid measure is adjusted into 250 parts, drop into 50 parts in sodium-chlor, crystallization is separated out, the crystallization that filtering separation is separated out is cleaned for 100 parts with 20% sodium chloride aqueous solution, obtains 22.6 parts of wet cakes.Be dissolved in water once more, total amount is adjusted into 250 parts, add 12.5 parts in sodium-chlor after being warming up to 60 ℃, add 35% aqueous hydrochloric acid the pH value is adjusted into 1.5, crystallization is separated out.The crystallization that filtering separation is separated out is cleaned for 200 parts with 20% sodium chloride aqueous solution, obtains 33.0 parts of wet cakes.33.0 parts of the wet cakes that obtained are dropped in 330 parts of the methyl alcohol, inject 33 parts in water, stir down in 60 ℃ and made its suspension after-filtration in 1 hour,, obtain 4.1 parts of blue crystallizations with methanol cleaning, drying.The λ max of this compound is 602.5nm (in the aqueous solution).

It is more than 75% that the β position of this compound replaces body, if infer from the input amount of reaction and formula (X-1) compound, for the m in the formula (9) (the position of substitution does not have appointment, represents with free acid form) is 3, n is 1 compound.But the result with the analysis of liquid chromatography mass analyzer also confirms to have sulfonic group.The analytical results that merges other infers that l value (sulfonic group) is about 0.3, the scope of n value (replacement sulfamyl) 0.3 to 1, thus inference all the other be m (not replacing sulfamyl), the summation of l, m and n is 4, near actual value.

Embodiment 3

Similarly to Example 1 phthalocyanine dye synthetic of formula (1) except in the pigment of the foregoing description 1, the β bit substituent being changed to 1 replacement sulfamyl that does not replace sulfamyl and 3 formulas (3)

In 100 parts of frozen water, drop into 17.6 parts of the copper phthalocyanine four SULPHURYL CHLORIDE wet cakes that embodiment 1 (2) obtained, stir and make its suspension.Maintain after 10 minutes and splash into 28% ammoniacal liquor below 5 ℃, the pH value is adjusted into 9.0.Then, in this suspension, inject 1.5 parts of ammoniacal liquor and 6.4 parts of water-soluble aqueous solution of 50 parts of formula (X-1) compound, the pH value is maintained 9.0, under 10 ℃, reacted 2 hours while add 28% ammoniacal liquor, under 20 ℃, reacted 2 hours, under 50 ℃, reacted 1 hour.Add entry, liquid measure is adjusted into 250 parts, drop into 50 parts in sodium-chlor, crystallization is separated out, the crystallization that filtering separation is separated out is cleaned for 100 parts with 20% sodium chloride aqueous solution, obtains 22.0 parts of wet cakes.Be dissolved in water once more, total amount is adjusted into 250 parts, add 50 parts in sodium-chlor after being warming up to 60 ℃, add 35% aqueous hydrochloric acid the pH value is adjusted into 1.0, crystallization is separated out.The crystallization that filtering separation is separated out is cleaned for 100 parts with 20% sodium chloride aqueous solution, obtains 21.7 parts of wet cakes.21.7 parts of the wet cakes that obtained are dropped in 220 parts of the methyl alcohol, inject 10 parts in water, stir down in 60 ℃ and made its suspension after-filtration in 1 hour,, obtain 5.8 parts of blue crystallizations with methanol cleaning, drying.The λ max of this compound is 612.0nm (in the aqueous solution).

It is more than 75% that the β position of this compound replaces body, if infer from the input amount of reaction and formula (X-1) compound, for the m in the formula (9) (the position of substitution does not have appointment, represents with free acid form) is 1, n is 3 compound.But the result with the analysis of liquid chromatography mass analyzer also confirms to have sulfonic group.The analytical results that merges other infers that l value (sulfonic group) is that about 0.3, n value (replacement sulfamyl) is 0.8 to 3, thus inference all the other be m (not replacing sulfamyl), the summation of l, m and n is 4, near actual value.

Embodiment 4

Similarly to Example 1 phthalocyanine dye synthetic of formula (1) except the replacement sulfamyl that in the pigment of the foregoing description 1, the replacement sulfamyl of formula (3) is changed to the amine that is derived from following (X-2)

(1) (Y is 4,6 to following formula (X-2) in the formula (X), and 8-three sulfo groups naphthalene-2-base-amino, Z are that amino, A are ethylidene, R ¹⁷, R ¹⁸Be the compound of hydrogen atom) synthetic

In 100 parts of frozen water, drop into 19.4 parts of Lipar OH0.6 part, cyanuryl chlorides, stirred 30 minutes.Then drop into 2-amino naphthalenes-4,6,74.5 parts of 8-trisulfonic acids (purity 51.4%) make the pH value maintain 2.7 to 3.0 Yi Bian add 25% aqueous sodium hydroxide solution, Yi Bian reacted 2 hours under 10 to 15 ℃, react 2 hours under in 25 to 30 ℃.Then, be cooled to this reaction solution below 5 ℃ after, add 25% aqueous sodium hydroxide solution, the pH value is adjusted into 10.0.In this reaction solution, add 12.1 parts of 28% ammoniacal liquor, reacted 2 hours under in 10 to 15 ℃, then reacted 2 hours under in 27 to 30 ℃.Liquid measure is adjusted into 700 parts, drops into 140 parts in sodium-chlor, then, add 35% hydrochloric acid the pH value is adjusted into 6, crystallization is separated out, filtering separation obtains 149.3 parts of wet cakes.149.3 parts of the wet cakes that obtained are dropped in 120 parts of the quadrols, under 80 ℃, reacted 1 hour.In reaction solution, drop into 900 parts of 2-propyl alcohol, carry out decant.In the residue that is obtained, drop into methyl alcohol and carry out crystallization for 1000 parts, filter,, obtain 27.7 parts of white crystals with methanol cleaning, drying.

(2) in 100 parts of frozen water, drop into 17.6 parts of the copper phthalocyanine four SULPHURYL CHLORIDE wet cakes that embodiment 1 (2) obtained, stir and make its suspension.Be maintained at after 10 minutes and splash into 28% ammoniacal liquor below 5 ℃, the pH value is adjusted into 9.0.Then, in this suspension, inject 1.0 parts of ammoniacal liquor and 5.8 parts of water-soluble aqueous solution of 50 parts of formula (X-2) compound, the pH value is maintained 9.0, under 10 ℃, reacted 2 hours while add 28% ammoniacal liquor, under 20 ℃, reacted 2 hours, under 50 ℃, reacted 1 hour.Add entry, liquid measure is adjusted into 200 parts, drop into 40 parts in sodium-chlor, crystallization is separated out, the crystallization that filtering separation is separated out is cleaned for 100 parts with 20% sodium chloride aqueous solution, obtains 28.3 parts of wet cakes.Be dissolved in water once more, total amount is adjusted into 200 parts, add 20 parts in sodium-chlor after being warming up to 60 ℃, add 35% aqueous hydrochloric acid the pH value is adjusted into 1.7, crystallization is separated out.The crystallization that filtering separation is separated out is cleaned for 100 parts with 10% sodium chloride aqueous solution, obtains 40.4 parts of wet cakes.40.4 parts of the wet cakes that obtained are dropped in 320 parts of the methyl alcohol, inject 16 parts in water, stir down in 60 ℃ and made its suspension after-filtration in 1 hour,, obtain 4.5 parts of blue crystallizations with methanol cleaning, drying.The λ max of this compound is 603.5nm (in the aqueous solution).

It is more than 75% that the β position of this compound replaces body, if infer from the input amount of the amine of reaction and formula (X-2), for the m in the formula (12) (the position of substitution does not have appointment, represents with free acid form) is 2, n is 2 compound.But the result with the analysis of liquid chromatography mass analyzer also confirms to have sulfonic group.The analytical results that merges other infers that l value (sulfonic group) is that about 0.3, n value (replacement sulfamyl) is 0.3 to 2, thus inference all the other be m, the summation of l, m and n is 4, near actual value.

Embodiment 5

Except the replacement sulfamyl that in the pigment of the foregoing description 1, the replacement sulfamyl of formula (3) is changed to the amine that is derived from following formula (X-3) similarly to Example 1 phthalocyanine dye synthetic of formula (1)

(1) (Y is 2 to following formula (X-3) in the formula (X), and 5-disulfobenzene amido, Z are that 2-sulfoethyl amine base, A are ethylidene, R ¹⁷, R ¹⁸Be the compound of hydrogen atom) synthetic

In 160 parts of frozen water, drop into 20 parts of Lipar OH0.1 part, cyanuryl chlorides, stirred 30 minutes.Then drop into aniline-2,33.2 parts of 5-disulfonate sodiums (purity 91.2%) make the pH value maintain 4.0 to 4.5 Yi Bian add 10% aqueous sodium carbonate, Yi Bian reacted 3 hours under 5 to 15 ℃.Then, in reaction solution, drop into 13.8 parts of 2-aminoethyl sulfonic acid,, reacted 0.5 hour under 15 ℃,, reacted 2 hours under 30 ℃ in pH8.0 to 8.5 in pH6.5 to 7.0.In 400 parts of reaction solutions,, separate out crystallization successively with 200 parts of 2-propyl alcohol and 60 parts of inputs of sodium-chlor.The crystallization of being separated out is filtered, clean, carry out drying under reduced pressure, obtain 130.2 parts of white crystals with the 2-propyl alcohol.Then, in 120 parts of quadrols, drop into 130.2 parts of the white crystals that obtained, under 80 ℃, reacted 1 hour.

In this reaction solution, drop into 800 parts of 2-propyl alcohol, carry out decant.In the residue that is obtained, drop into 600 parts of methyl alcohol with the residue dissolving, carry out liquid filtering, drop into the 2-propyl alcohol in the filtrate and 1200 parts crystallization is separated out.The crystallization that filtering separation is separated out, clean, dry with the 2-propyl alcohol, obtain 41.0 parts of white crystals.

(2) in 100 parts of frozen water, drop into 17.6 parts of the copper phthalocyanine four SULPHURYL CHLORIDE wet cakes that embodiment 1 (2) obtained, stir and make its suspension.Maintain after 10 minutes and splash into 28% ammoniacal liquor below 5 ℃, the pH value is adjusted into 9.0.Then, in this suspension, inject 1.0 parts of ammoniacal liquor and 5.1 parts of water-soluble aqueous solution of 50 parts of formula (X-3) compound, the pH value is remained on 9.0, under 10 ℃, reacted 2 hours by adding 28% ammoniacal liquor, under 20 ℃, reacted 2 hours, under 50 ℃, reacted 1 hour.Add entry, liquid measure is adjusted into 200 parts, drop into 40 parts in sodium-chlor, crystallization is separated out, the crystallization that filtering separation is separated out is cleaned for 100 parts with 20% sodium chloride aqueous solution, obtains 25.3 parts of wet cakes.Be dissolved in water once more, total amount is adjusted into 200 parts, add 40 parts in sodium-chlor after being warming up to 60 ℃, then, add 35% aqueous hydrochloric acid the pH value is adjusted into 1.0, crystallization is separated out.The crystallization that filtering separation is separated out is cleaned for 100 parts with 20% sodium chloride aqueous solution, obtains 22.1 parts of wet cakes.22.1 parts of the wet cakes that obtained are dropped in 220 parts of the methyl alcohol, inject 11 parts in water, stir down in 60 ℃ and made its suspension after-filtration in 1 hour,, obtain 5.3 parts of blue crystallizations with methanol cleaning, drying.The λ max of this compound is 608.5nm (in the aqueous solution).

It is more than 5% that the β position of this compound replaces body, if infer from the input amount of the amine of reaction and formula (X-3), for the m in the formula (13) (the position of substitution does not have appointment, represents with free acid form) is 2, n is 2 compound.But the result with the analysis of liquid chromatography mass analyzer also confirms to have sulfonic group.The analytical results that merges other infers that l value (sulfonic group) is that about 0.3, n value is 0.5 to 2, thus inference all the other be m (not replacing sulfamyl), the summation of l, m and n is 4, near actual value.

Embodiment 6

Similarly to Example 1 phthalocyanine dye synthetic of formula (1) except in the pigment of the foregoing description 1, the β bit substituent being changed to 2.5 replacement sulfamyl that do not replace sulfamyl and 1.5 formulas (3)

In 100 parts of frozen water, drop into 17.6 parts of the copper phthalocyanine four SULPHURYL CHLORIDE wet cakes that embodiment 1 (2) obtained, stir and make its suspension.Inject 1.0 parts of ammoniacal liquor and 3.2 parts of water-soluble aqueous solution of 60 parts of formula (X-1) compound after 10 minutes, the pH value is remained on 8 to 8.5, reacted 9 hours under in 17 to 20 ℃ while add 28% ammoniacal liquor.Add entry, liquid measure is adjusted into 250 parts, drop into 50 parts in sodium-chlor, crystallization is separated out, the crystallization that filtering separation is separated out is cleaned for 100 parts with 20% sodium chloride aqueous solution, obtains 22.6 parts of wet cakes.Be dissolved in water once more, total amount is adjusted into 250 parts, add 12.5 parts in sodium-chlor after being warming up to 60 ℃, add 35% aqueous hydrochloric acid the pH value is adjusted into 1.5, crystallization is separated out.The crystallization that filtering separation is separated out is cleaned for 200 parts with 20% sodium chloride aqueous solution, obtains 33.0 parts of wet cakes.33.0 parts of the wet cakes that obtained are dropped in 330 parts of the methyl alcohol, inject 33 parts in water, stir down in 60 ℃ and made its suspension after-filtration in 1 hour,, obtain 4.1 parts of blue crystallizations with methanol cleaning, drying.The λ max of this compound is 612.1nm (in the aqueous solution).

It is more than 75% that the β position of this compound replaces body, if infer from the input amount of reaction and formula (X-1) compound, for the m in the formula (9) (the position of substitution does not have appointment, represents with free acid form) is 3, n is 1 compound.But the result with the analysis of liquid chromatography mass analyzer also confirms to have sulfonic group.The analytical results that merges other infers that l value (sulfonic group) is that about 0.2, n value (replacement sulfamyl) is 0.8 to 1.5, thus inference all the other be m (not replacing sulfamyl) (about 2.8 to 3), the summation of l, m and n is 4, near actual value.

Embodiment 7 (ink evaluation)

(A) adjustment of printing ink

With each composition mixed dissolution that following table 8 is disclosed, membrane filter (manufacturing of the Advantec company) filtration with 0.45 μ m obtains printing ink.In addition, water uses ion exchanged water.The pH=8 to 10 of printing ink, adding entry, caustic soda (pH adjusts agent), to make total amount be 100 parts.Printing ink use embodiment 1 compound printing ink be numbered C-1, use its each self-corresponding C-2 to C-6 that is numbered of printing ink of embodiment 2 to 6 compounds.

Table 8

1.3 parts of each compounds that the foregoing description 1 to 6 is obtained

79.6 parts in water+caustic soda

5.0 parts of glycerine

5.0 parts in urea

4.0 parts of N-N-methyl-2-2-pyrrolidone N-s

3.0 parts of IPA (Virahol)

2.0 parts of diethylene glycol monobutyl ethers

0.1 part of Surfinol 104PG50 (trade(brand)name: a day letter chemical company makes)

Add up to 100.0 parts

As a comparative example, with ink-vapor recording pigment, goods name: Projet Cyan 1 (the Abesia company manufacturing generally used as sun blue 199; Comparative example 1) and the method that is disclosed with above-mentioned document 8 embodiment 1 is synthetic and the colorant mixture (comparative example 2) of purifying makes with the printing ink of table 1 embodiment 1 to 6 with same method adjustment when printing identical printing concentration is arranged.Use the printing ink of the goods of comparative example 1 to be C-A, use the printing ink of the compound of comparative example 2 to be C-B.

(B) ink-jet printer

Use ink-jet printer (trade(brand)name Canon Inc. makes BJ S630), carry out ink-vapor recording for 2 kinds in glossy paper A (the manufacturing PM of Seiko Epson Corporation takes pictures and uses paper KA420PSK), glossy paper B (Canon Inc. makes professional photo paper PR-101).

(C) evaluation of document image

1. tone evaluation

The tone of document image is that recording paper is carried out colour examining with chromatic measuring system (manufacturing of GRETAG SPM50:GRETAG company), measures the L of print ^*A when 50 to 90 scopes ^*, b ^*Value.With ideal a ^*Value defined is-50 to-10, b ^*Value defined is-50 to-10, is divided into for 3 stages to estimate.

Zero: a ^*, b ^*Value is present in the favored area simultaneously

△: a ^*, b ^*Value has only a side to be present in the favored area

*: a ^*, b ^*Value is present in outside the favored area simultaneously

2. light fastness test

With document image test film xenon arc lamp weather resistance test device (ATLAS corporate system moulding formula Ci4000), with irradiation under the condition of 0.36W/ square centimeter illumination 24 ℃ of temperature, humidity 60%RH in groove 50 hours.Test back reflection concentration (D value) is carried out colour examining with the reflection density before and after the test with above-mentioned chromatic measuring system in 0.70 to 0.85 scope.Measure the back with (reflection density before the reflection density/test after the test) * 100 (%) calculating pigment survival rate, be divided into for 3 stages to estimate.

Zero: survival rate is more than 70%

△: survival rate is 50 to 70%

*: survival rate is less than 50%

3. ozone resistance test

With document image test film ozone weather resistance test device (Suga trier corporate system moulding formula OMS-H), to place 3 hours under the condition of 24 ℃ of temperature in ozone concn 12ppm, the groove, humidity 60%RH.Test back reflection concentration (D value) is carried out colour examining with the reflection density before and after the test with above-mentioned chromatic measuring system in 0.70 to 0.85 scope.Measure the back with (reflection density before the reflection density/test after the test) * 100 (%) calculating pigment survival rate, be divided into for 3 stages to estimate.

Zero: survival rate is more than 70%

△: survival rate is 40 to 70%

*: survival rate is less than 40%

4. anti-moisture test

The document image test film with controlled thermohygrostat (use skill and grind the manufacturing of industry company), was placed 3 under the condition of 50 ℃ of temperature, humidity 90%RH in groove.The bleeding of test back test film was divided into for 3 stages and estimates with visual.

Zero: confirm no bleeding

△: confirm a little bleeding

*: confirm to have big bleeding

Use tone assessment, light fastness test result, ozone resistance test-results and the anti-moisture test result of printing ink (C-1 to the C-6) document image of embodiment 1 to 6 compound that obtains to be shown in table 9 (glossy paper A) and table 10 (glossy paper B) respectively.

Table 9

Printing ink assessment result: glossy paper A

Printing ink numbering tone photostabilization ozone resistance wet fastness

C-1 ○ ○ ○ ○

C-2 ○ ○ ○ ○

C-3 ○ ○ ○ ○

C-4 ○ ○ ○ ○

C-5 ○ ○ ○ ○

C-6 ○ ○ ○ ○

C-A ○ ○ × ○

C-B ○ ○ × ○

Table 10

Printing ink assessment result: glossy paper B

Printing ink numbering tone photostabilization ozone resistance wet fastness

C-1 ○ ○ ○ ○

C-2 ○ ○ ○ ○

C-3 ○ ○ ○ ○

C-4 ○ ○ ○ ○

C-5 ○ ○ ○ ○

C-6 ○ ○ ○ ○

C-A ○ ○ × ○

C-B ○ ○ × ○

Use the cyan ink of The compounds of this invention superior as can be known from table 9 and table 10, the printing ink that photostabilization, ozone resistance and wet fastness are superior as tone.Especially ozone resistance is superior.

Embodiment 8 (printing ink group)

Go up installation pale cyan ink C-1 in the ink-jet printer with the cyan ink group that is set with nattierblue and 2 kinds of concentration of darkcyan (trade(brand)name Canon Inc. makes BJ F850), the pure cyan ink of making as the Canon Inc. of darkcyan printing ink carries out ink-vapor recording for 2 kinds at glossy paper A (Seiko Epson Corporation make PM take pictures use paper KA420PSK), glossy paper B (Canon Inc. makes professional photo paper PR-101).Print result obtains can not produce round dot and omits, also obtains as the full-colour image printing the distinct print that satisfies.This results verification printing ink of the present invention also can be used for having the ink-jet printer of the cyan ink group that is set with nattierblue and 2 kinds of concentration of darkcyan.

[possibility of utilizing on the industry]

The printing ink that uses The compounds of this invention as cyan ink etc. for having good tone, anti-The printing ink that photosensitiveness, ozone resistance and moisture-proof are superior. Also do not have after long-time the preservation crystallization, Rerum natura variation, look variation etc., bin stability is good. In addition, with other magenta ink and Huang Color ink uses the tone that can access extensive viewing area simultaneously. Therefore, use phthalocyanine of the present invention The printing ink of pigment, especially cyan ink, very useful as the printing ink that ink mist recording is used.

Claims

1. the phthalocyanine dye of formula (1) expression,

In the formula (1), M is hydrogen atom, atoms metal, metal oxide, metal hydroxides or metal halide, R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄, R ₁₅Independent separately is the not replacement sulfamyl of formula (2) expression, the replacement sulfamyl or the hydrogen atom of formula (3) expression; Wherein, R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄, R ₁₅In have 1 at least for not replacing sulfamyl, have 1 replacement sulfamyl at least for formula (3) expression; In addition, R ₁, R ₄, R ₅, R ₈, R ₉, R ₁₂, R ₁₃, R ₁₆Be hydrogen atom; Do not replace the sulphonamide radix with replace the sulphonamide radix and be 2 to 4, and not replace the sulphonamide radix be 1 to 3, replacing the sulphonamide radix is 1 to 3,

-SO ₂NH ₂ (2)

In the formula (3), R ₁₇And R ₁₈Independent separately is hydrogen atom, A is the alkylidene group of carbonatoms 1 to 4, Y and Z either party are amino or by the alkylamino of the C1 to C6 of sulfonic group or carboxyl substituted, and the opposing party is by the phenylamino of sulfonic group or carboxyl substituted or by the naphthylamino of sulfonic group or carboxyl substituted.

2. phthalocyanine dye as claimed in claim 1, it is formula (4) expression of Cu by M in the formula (1),

R in the formula ₁To R ₁₆With synonym in the formula (1).

3. phthalocyanine dye as claimed in claim 1 or 2, wherein, at R ₂With R ₃, R ₆With R ₇, R ₁₀With R ₁₁, R ₁₄With R ₁₅Each combination in, a side separately be a hydrogen atom, the opposing party is the not replacement sulfamyl represented of formula (2), replacement sulfamyl or the hydrogen atom that formula (3) is represented, and R ₂, R ₃, R ₆, R ₇, R ₁₀, R ₁₁, R ₁₄, R ₁₅In have 1 at least for not replacing sulfamyl, have 1 replacement sulfamyl at least for formula (3) expression.

4. phthalocyanine dye, wherein, the pigment content of following formula (1) all is at least more than 60% with respect to pigment,

-SO ₂NH ₂ (2)

In the formula (3), R ₁₇And R ₁₈Independent separately is hydrogen atom, A is the alkylidene group of carbonatoms 1 to 4, Y and Z either party are amino or by the alkylamino of the C1 to C6 of sulfonic group or carboxyl substituted, the opposing party be by the phenylamino of sulfonic group or carboxyl substituted or, by the naphthylamino of sulfonic group or carboxyl substituted.

5. phthalocyanine dye as claimed in claim 1 or 2, wherein, formula (1) is to react by the phthalocyanine dye that makes formula (6) expression or its salt and chlorizating agent, and sulfonic group is converted to the chlorsulfonic acid base, react with the organic amine of following formula (X) expression and amidating agent then and obtain

In the formula (6), M is hydrogen atom, metallic element, metal oxide, metal hydroxides or metal halide, and L is the ion or the ammonium ion of proton, alkalimetal ion, alkaline-earth metal ions, organic amine, and a, b, c, d are 0 or 1, itself and be 2 to 4 integer,

In the formula (X), R ₁₇And R ₁₈Independent separately is hydrogen atom, A is the alkylidene group of carbonatoms 1 to 4, Y and Z either party are amino or by the alkylamino of the C1 to C6 of sulfonic group or carboxyl substituted, and the opposing party is by the phenylamino of sulfonic group or carboxyl substituted or by the naphthylamino of sulfonic group or carboxyl substituted.

6. phthalocyanine dye as claimed in claim 5, wherein, M is a copper.

7. printing ink is characterized in that, contains in the claim 1 to 6 each described phthalocyanine dye as pigment composition.

8. printing ink as claimed in claim 7, it contains organic solvent.

9. printing ink as claimed in claim 7, wherein, this printing ink is that ink-vapor recording is used.

10. the printing ink group is characterized in that, in using the different ink-jet printer of cyan ink more than 2 kinds of pigment concentration, uses the described printing ink of at least a claim 7.

11. ink jet recording method is characterized in that, in discharging ink droplet corresponding record signal with the ink jet recording method that is being recorded the enterprising line item of material, uses the described printing ink of claim 7.

12. ink jet recording method as claimed in claim 11 wherein, is recorded material and is information transmission sheet material.

13. ink jet recording method as claimed in claim 12, wherein, information transmission sheet material is surface treated sheet material, and has the ink-receiver layer that contains the white inorganic pigment particle on support.

14. colouring agent, it is painted with the described printing ink of claim 7.

15. the manufacture method of the phthalocyanine dye of the described formula of claim 2 (4) expression, in the formula (4), R ₂And R ₃, R ₆And R ₇, R ₁₀And R ₁₁, R ₁₄And R ₁₅In each combination; a side is a hydrogen atom respectively; the opposing party is the replacement sulfamyl that the nothing of formula (2) expression replaces sulfamyl or formula (3) expression; it is characterized in that; be selected from 4-sulfo group phthalic acid by making; 4-sulfo group phthalate anhydride; the 4-sulfophthalimide; 4-sulfo group phthalonitrile; 4-or 5-sulfo group-2-cyano group benzamide and 5-sulfo group-1; compound in 3-diimino isoindoline or their salt reacts in the presence of copper compound; obtain compound or its salt; itself and chlorizating agent are reacted change sulfonic group into the chlorsulfonic acid base, require the organic amine of 5 described formulas (X) expressions and amidating agent to react with aforesaid right then and obtain this phthalocyanine dye.