CN1961049A - Ink composition, method of ink-jet recording with the same, and recording object - Google Patents

Abstract

The invention improves non-clogging properties and suitability for ink droplet deflection. An ink composition comprising water, a colorant, and an aromatic compound having a carboxy group, characterized by containing at least one member selected from the group consisting of sodium, potassium, and ammonium ions and further containing lithium ions; or an ink composition comprising water, a specific cyan dye, and an aromatic compound having a carboxy group, characterized by containing lithium ions and sodium and/or potassium ions.

Description

Ink composition, inkjet recording method using same, and recorded matter

technical field

The present invention relates to an inkjet composition suitable for inkjet recording, in particular, it is excellent in fastness of printed matter (mainly gas resistance, light resistance, moisture resistance), copper light floating resistance (bronze resistance), and is excellent in clogging. An ink composition with improved recovery and ink droplet deflection countermeasures, an inkjet recording method using the ink composition, and a recorded matter recorded by the recording method.

Background technique

Inkjet recording is a method of ejecting an ink composition as droplets from fine nozzles to record characters or images (hereinafter, sometimes simply referred to as "images") on the surface of a recording medium. As an inkjet recording method, there are practical applications: using electrostrictive elements to convert electrical signals into mechanical signals, intermittently ejecting the ink composition stored in the nozzle head part, and recording characters or images on the surface of the recording medium. ; The method of rapidly heating the ink composition stored in the nozzle head part very close to the ejection part to generate bubbles, and using the volume expansion caused by the bubbles to eject intermittently, recording characters or images on the surface of the recording medium, etc.

In addition, from the aspects of safety and printing characteristics, the ink composition for inkjet recording is usually an ink composition obtained by dissolving various dyes in water or an organic solvent or a mixture thereof. In terms of ink compositions for writing instruments such as fountain pens and ballpoint pens, stricter conditions are required.

In recent years, inkjet printers have begun to be used for producing printed materials for advertisements. Since the produced printed matter is placed not only indoors but also outdoors, high image retention is required. Since printed matter is exposed to various types of light including sunlight and outside air (ozone, nitrogen oxides, sulfur oxides, etc.), an ink composition excellent in light resistance and gas resistance has been developed.

Among cyan dyes, a cyan ink composition having excellent light resistance and gas resistance by improvement of metal phthalocyanine dyes has been developed (for example, refer to International Publication No. 02/060994 pamphlet). However, in metal phthalocyanine-based dyes with improved gas resistance, redness may be seen on parts printed with high coverage such as solid printing (full printing with 100% coverage) (hereinafter referred to as "Copper Floating Phenomenon"). In this case, the color balance of the image as a whole becomes non-uniform, which lowers the image quality, and thus needs to be improved.

In addition, in recent years, glossy paper has been widely used as a recording medium with a style similar to that of photographs, but due to the coppery floating phenomenon caused by specific colors, there is a difference in the glossiness on the surface of the printed matter, which obviously damages the style of the image, so from From the viewpoint of maintaining the uniform glossiness of the entire image, there is also a strong demand for improvement.

With regard to the light fastness ability, the ability of the magenta ink composition is the lowest, and it often becomes the reason for controlling the light fastness life of the ink cartridge. Therefore, a magenta ink composition with excellent light fastness and gas resistance has also been developed (refer to Japanese Patent Laid-Open 2002- 371079 bulletin), but also need to improve moisture resistance.

As a means to solve these problems, the present inventors proposed to contain an aromatic compound having a carboxyl group in the ink composition (Japanese Patent Application No. 2002-254611 specification, Japanese Patent Application No. 2003-090345 specification, Japanese Patent Application No. number manual). It was confirmed that if the above-mentioned aromatic composition having a carboxyl group contains lithium hydroxide as a lithium salt or a neutralizing agent, the effect of improving the coppery floating phenomenon is remarkably excellent, and the eye-clogging resistance is also remarkably good.

In these embodiments, the printer is used in a correct state, and after the printing is completed, the print head returns to the initial position and is covered for the next printing. Under such conditions, sufficient anti-clogging properties are ensured.

Contents of the invention

However, when the printer loses power supply during printing, the print head is still at a non-starting position, often placed in an uncovered state. Under this condition, even in the above-mentioned embodiment, clogging due to precipitation of lithium salt of the aromatic composition having a carboxyl group occurs, and ink drop bending due to corrosion and peeling of the orifice plate occurs, and there is further improvement. room for.

Therefore, the object of the present invention is to provide a product that does not degrade the image quality (bronze flooding resistance) and image preservation (light resistance, gas resistance, moisture resistance), and further prevents clogging and ink bending, etc., and the quality reliability is improved. An improved ink composition, and an inkjet recording method and recorded matter using the ink composition.

The present inventors found that by (A) containing lithium ions together with the above-mentioned aromatic compound having a carboxyl group, and containing at least one selected from sodium ions, potassium ions, and ammonium ions in the ink composition; and ( B) When the colorant is the specific cyan dye of the present invention, sodium ions and/or potassium ions are contained in the ink composition together with the above-mentioned carboxyl group, or lithium ions are contained as counter cations of the cyan dye. , thereby preventing precipitation of the lithium salt of the aromatic compound having a carboxyl group. Furthermore, they also found that the effect of preventing lithium salt precipitation increases when urea is further contained, and completed the present invention based on this knowledge.

That is, the present invention has the following configurations.

Inventions consisting of concepts under (A), namely

1. An ink composition comprising at least water, a colorant, and an aromatic compound having a carboxyl group, characterized by containing at least one selected from the group consisting of sodium ions, potassium ions, and ammonium ions, and lithium ions.

and inventions constituted by the concepts of (B), namely

2. An ink composition comprising at least water and a cyan dye represented by the following general formula (I) and an aromatic compound having a carboxyl group, characterized in that it contains lithium ions, sodium ions and/or or potassium ions.

Taking the general formula (I) as its main focus, it consists of them and the following subordinate inventions.

[chemical 1]

General formula (I)

(In the formula, each of X ₁ , X ₂ , X ₃ and X ₄ independently represents any one of -SO-Z and -SO ₂ -Z. Here, each of Z independently represents substituted or unsubstituted alkyl, substituted or unsubstituted A substituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently representing a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, Amino, alkylamino, alkoxy, aryloxy, amido, arylamino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl, alkane Oxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonyl, aryloxycarbonylamino, imino, heterocyclic thio, phosphoryl , an acyl group, or an ionic hydrophilic group, and each group may further have a substituent.

a ₁ to a ₄ and b ₁ to b ₄ represent the numbers of substituents of X ₁ to X ₂ and Y ₁ to Y ₄ , respectively. a ₁ to a ₄ are each independently an integer of 0 to 4, and are not 0 at the same time. b ₁ to b ₄ are each independently an integer of 0-4.

M represents a hydrogen atom, a metal element or its oxide, hydroxide or halide.

However, at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ and Y ₄ is an ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent group. )

3. The ink composition according to 2, wherein the cyan dye represented by the general formula (I) is represented by the following general formula (II).

[Chem 2]

General formula (II)

(In the formula, M has the same meaning as in the general formula (I), R ₁ to R ₄ each independently represent -SO ₂ Z. Z has the same meaning as in the general formula (I). However, at least one of the 4 Z has an ion hydrophilic groups as substituents.)

4. The ink composition according to 3, wherein M in the above general formula (II) of the cyan dye is copper element, and Z having an ionic hydrophilic group is a sulfoalkyl group.

5. The ink composition according to 4, wherein the counter cation of the sulfoalkyl group is a lithium cation.

6. The ink composition according to any one of 1 to 5, further comprising urea.

7. The ink composition according to 6, wherein the urea is contained in an amount of 1 to 6% by weight of the ink composition.

8. The ink composition according to any one of 1, 6, and 7, wherein, with respect to the aromatic compound having a carboxyl group, at least one selected from sodium ions, potassium ions, and ammonium ions and lithium The total molar ratio of ions is 1:5-10:8.

9. The ink composition according to 8, wherein the molar ratio of lithium ions to at least one kind selected from sodium ions, potassium ions and ammonium ions is 8:1 to 1:1.

10. The ink composition according to any one of 2 to 7, wherein the moles of lithium ions are The number is 1.2 times or more, and the total number of moles of sodium ions and potassium ions is 0.7 times or less.

11. The ink composition according to any one of 2-7, 10, characterized in that, relative to the moles of carboxyl groups of the aromatic compound having carboxyl groups, the total mole number of sodium ions and potassium ions is 0.3 more than double.

12. The ink composition according to any one of 2 to 7 and 10 to 11, wherein the number of moles of the sulfoalkyl group having an ionic hydrophilic group relative to the cyan dye and The sum of the carboxyl moles of the aromatic compounds having carboxyl groups is 0.8 to 1.2 times the total moles of lithium ions, sodium ions, and potassium ions.

13. The ink composition according to any one of 1 to 12, wherein the aromatic compound having a carboxyl group is an aromatic compound having one carboxyl group.

14. The ink composition according to any one of 1 to 13, wherein the aromatic compound having a carboxyl group is a compound having a naphthalene skeleton.

15. The ink composition according to 14, wherein the compound having a naphthalene skeleton is a compound having a carboxyl group at the 2-position.

16. The ink composition according to 15, wherein the compound having a carboxyl group at the 2-position and having a naphthalene skeleton is 1-hydroxy-2-naphthoic acid, 2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6-Hydroxy-2-naphthoic acid, 3-methoxy-2-naphthoic acid, 6-methoxy-2-naphthoic acid, 6-ethoxy-2-naphthoic acid, 6-propoxy-2- At least one kind of naphthoic acid.

17. The ink composition according to any one of 1 to 16, wherein the aromatic compound having a carboxyl group is contained in an amount of 0.1 to 10% by weight based on the total amount of the ink composition.

18. The ink composition according to any one of 1 to 17, wherein the content ratio of the colorant (including the cyan dye) and the aromatic compound having a carboxyl group is 1 in weight ratio. : the range of 0.2 to 1:10.

19. The ink composition according to any one of 1 to 18, which is used in an inkjet recording method.

20. The ink composition according to 19, wherein the inkjet recording method is a recording method using an inkjet head that forms ink droplets using mechanical deformation of an electrostrictive element.

21. An inkjet recording method, the recording method is an inkjet recording method in which droplets of an ink composition are ejected, and the droplets are attached to a recording medium for recording, wherein any one of 1 to 20 is used. The ink composition is used as an ink composition.

22. A recorded matter, which is recorded using the ink composition described in any one of 1 to 20, or recorded by the recording method described in 21.

According to the present invention, since the lithium salt of an aromatic compound having a carboxyl group in the ink composition is prevented from being precipitated, it is possible to provide high image quality (patina resistance) and image preservation (light resistance and gas resistance) without deteriorating. performance, moisture resistance), and an ink composition with improved reliability in clogging and ink droplet deflection, and an inkjet recording method and recorded matter using the ink composition.

Detailed ways

The invention of the above-mentioned concept (A) is an ink composition containing at least a colorant and an aromatic compound having a carboxyl group in water or an aqueous medium containing water and a water-soluble organic solvent, which contains sodium ions, potassium ions, and At least one kind of ammonium ion and lithium ion.

The invention of the concept (B) above is an ink composition comprising at least a cyan dye represented by the above general formula (I) and an aromatic compound having a carboxyl group in water or an aqueous medium composed of water and a water-soluble organic solvent. , which contain lithium ions and sodium ions and/or potassium ions.

In any of the above-mentioned inventions, urea may be further contained as needed, and a humectant, a viscosity modifier, a pH modifier, or other additives may also be contained.

First, the coloring agent used in the inventive form of (A) concept is demonstrated.

The coloring agent used in the present invention tends to cause copper floating, but any coloring agent may be used as long as it eliminates copper floating by an aromatic compound having a carboxyl group. Furthermore, it is preferable to use a copper phthalocyanine coloring agent. Direct blue 199 is mentioned as a copper phthalocyanine coloring agent.

In addition, although the image fastness such as light resistance and gas resistance is excellent, the moisture resistance is poor, as long as the aromatic compound having a carboxyl group has improved moisture resistance, any coloring agent may be used.

Specific examples of such magenta dyes include compounds represented by the following formula (1) and salts thereof.

Formula 1)

[Chem 3]

General formula (I)

(R表示氢或烷基)，X表示NH₂、OH或Cl。][In the formula (1), A represents an alkylene group, an alkylene group containing a phenylene group or

(R represents hydrogen or alkyl), X represents NH ₂ , OH or Cl. ]

The compound represented by the above formula (1) and its salt can be produced by any method, for example, it can be produced by the following method.

1) Reaction of ethyl benzoylacetate with 1-methylamino-4-bromoanthraquinone in a solvent to obtain 1-benzoyl-6-bromo-2,7-dihydro-3-methyl-2 , 7-dioxo-3H-dibenzo[f,ij]isoquinoline.

2) Next, react the compound obtained in the above 1) with m-aminoacetanilide in a solvent to obtain 3'-[1-benzoyl-2,7-dihydro-3-methyl-2,7- Dioxo-3H-dibenzo[f,ij]isoquinolin-6-ylamino]-acetanilide.

3) Next, the compound obtained in the above 2) is reacted in oleum to obtain 6-amino-4-[2,7-dihydro-3-methyl-1-(3-sulfonated benzoyl )-2,7-dioxo-3H-dibenzo[f,ij]isoquinolin-6-ylamino]-benzene-1,3-disulfonate trisodium.

4) Next, the compound obtained in the above 3) is reacted with cyanuric chloride in water to obtain a primary condensate, and the primary condensate is reacted with a diamine having a linker A to obtain a secondary condensate.

5) Next, the compound obtained in the above 4) is hydrolyzed as it is or reacted with ammonia to form a tertiary condensate to obtain the target compound represented by the above formula (1).

As the coloring agent used in the ink composition of the present invention, one of the compounds represented by the above formula (1) and salts thereof may be selected and used alone, or a plurality of them may be selected and used.

The magenta ink composition containing at least one compound selected from the group consisting of the compound represented by the above formula (1) and its salts is superior in light resistance compared to a magenta ink composition containing a conventional magenta dye.

Moreover, the compound represented by the following formula (2) also has the effect of improving light resistance and gas resistance, and may be used individually by 1 type, and may use multiple types together.

Formula (2)

[chemical 5]

[In the above formula (2), A represents the residue of the 5-membered heterocyclic diazo component A-NH ₂ . B ¹ and B ² respectively represent -CR ¹ =, -CR ² =, or one of them represents a nitrogen atom, and the other represents -CR ¹ = or -CR ² =. R ⁵ and R ⁶ are each independently representing hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group acyl or sulfamoyl. Each group may further have a substituent. G, R ¹ , and R ² are each independently representing a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Acyl, hydroxy, alkoxy, aryloxy, silyloxy, acyloxy, carbamoyloxy, heterocyclic oxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl or Aryl or heterocyclic substituted amino, amido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkyl and arylsulfonylamino, nitro, alkyl and aryl Thio, alkyl and arylsulfonyl, alkyl and arylsulfinyl, sulfamoyl, sulfo or heterocyclicthio. Each group may be substituted. Exceptionally, R ¹ and R ⁵ or R ⁵ and R ⁶ can also combine to form a 5-6 membered ring. ]

Hereinafter, the compound represented by the formula (2) which can be used as a coloring agent in this invention is demonstrated.

In formula (2), A represents the residue of the 5-membered heterocyclic diazo component A-NH ₂ . N, O and S can be mentioned as examples of the hetero atom of the 5-membered heterocyclic ring. It is preferably a nitrogen-containing 5-membered heterocyclic ring, and an aliphatic ring, an aromatic ring, or other heterocyclic rings may also be condensed on the heterocyclic ring. Examples of preferred heterocyclic rings for A include pyrazole rings, imidazole rings, thiazole rings, isothiazole rings, thiadiazole rings, benzothiazole rings, benzoxazole rings, and benzisothiazole rings. Each heterocyclic group may further have a substituent. Among them, pyrazole rings, imidazole rings, isothiazole rings, thiadiazoles, and benzothiazole rings represented by the following (a) to (f) are preferable.

general formula

[chemical 6]

R ⁷ to R ²⁰ in the above general formulas (a) to (f) represent the same substituents as substituents G, R ¹ and R ² described later. Among the general formulas (a) to (f), pyrazole rings and isothiazole rings represented by general formulas (a) and (b) are preferred, and pyrazole rings represented by general formula (a) are most preferred.

B ¹ and B ² represent -CR ¹ =, -CR ² = respectively, or one of them represents nitrogen, and the other represents -CR ¹ = or -CR ² =, but more preferably represents -CR ¹ =, -CR respectively ² =.

R ⁵ and R ⁶ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl group and an arylsulfonyl group, or a sulfamoyl group, and each group may have a substituent. Preferred substituents represented by R ⁵ and R ⁶ include hydrogen atoms, aliphatic groups, aromatic groups, heterocyclic groups, acyl groups, alkyl groups and arylsulfonyl groups. More preferably, it is a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl group or an arylsulfonyl group. Most preferred are hydrogen atom, aryl group and heterocyclic group. Each substituent may have a substituent further. However, R ⁵ and R ⁶ are not hydrogen atoms at the same time.

G, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Acyl, hydroxy, alkoxy, aryloxy, silyloxy, acyloxy, carbamoyloxy, heterocyclyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl or Aryl or heterocyclic substituted amino, acylamino, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkyl and arylsulfonylamino, nitro, alkyl and aryl Thio, heterocyclicthio, alkyl and arylsulfonyl, alkylsulfinyl, arylsulfinyl, sulfamoyl or sulfo, the individual groups may also be substituted.

Preferred substituents represented by G include hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxyl group, alkoxy group, aryloxy group, acyloxy group, heterooxyl group, alkyl group, etc. Or aryl or heterocyclic substituted amino, acylamino, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkyl and arylthio and heterocyclicthio. More preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group or an amido group substituted by an alkyl group, an aryl group or a heterocyclic group, among which a hydrogen atom, an aromatic group Amino, amido. Each substituent may have a substituent further.

Preferred substituents represented by R ¹ and R ² include a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, and a cyano group. Each substituent may have a substituent further. R ¹ and R ⁵ or R ⁵ and R ⁶ may combine to form a 5-6 membered ring. Examples of substituents when each of the substituents represented by A, R ¹ , R ² , R ⁵ , R ⁶ , and G further have substituents include the substituents mentioned above for G, R ¹ , and R ² .

When the azo dye represented by formula (2) is a water-soluble dye, it is preferable to further have an ionic hydrophilic group as a substituent at any position of A, R ¹ , R ² , R ⁵ , R ⁶ , and G . The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, a quaternary ammonium group, and the like. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl and sulfo groups may be in the form of salts, and examples of counterions that form salts include alkali metal ions (for example, sodium ions, potassium ions, lithium ions), ammonium ions, and organic cations (for example, tetramethylammonium, tetramethylammonium, Guanidine ion).

Hereinafter, the substituents represented by G, R ¹ and R ² will be described in detail.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

In the present specification, the aliphatic group refers to an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group. Aliphatic groups may have branched chains or form rings. The number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-16. Aralkyl and the aryl part of substituted aralkyl are preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, tert-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl , 4-sulfobutyl, cyclohexyl, benzyl, 2-phenethyl, vinyl and allyl.

In this specification, an aromatic group refers to an aryl group and a substituted aryl group. Aryl is preferably phenyl or naphthyl, particularly preferably phenyl. The number of carbonyl atoms in the aromatic group is preferably 6-20, more preferably 6-16. Examples of aromatic groups include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m-(3-sulfopropylamino)phenyl. The heterocyclic group includes a substituted heterocyclic group and an unsubstituted heterocyclic group. It is also possible to condense aliphatic rings, aromatic rings or other heterocyclic rings on heterocyclic rings. The heterocyclic ring is preferably a 5-membered or 6-membered heterocyclic ring. Examples of substituents include aliphatic groups, halogen atoms, alkyl and arylsulfonyl groups, acyl groups, amido groups, sulfamoyl groups, carbamoyl groups, ionic hydrophilic groups and the like. Examples of the heterocyclic group include 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-benzothiazolyl, 2-benzoxazolyl and 2-furyl.

The carbamoyl group includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of substituents include alkyl groups. Examples of the carbamoyl group include methylcarbamoyl and dimethylcarbamoyl.

The alkoxycarbonyl group includes a substituted alkoxycarbonyl group and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms. Examples of substituents include ionic hydrophilic groups. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.

The aryloxycarbonyl group includes substituted aryloxycarbonyl groups and unsubstituted aryloxycarbonyl groups. As the aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 12 carbon atoms is preferable. The substituent includes an ionic hydrophilic group. Examples of the aryloxycarbonyl group include phenoxycarbonyl.

The acyl group includes a substituted acyl group and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms. Examples of substituents include ionic hydrophilic groups. Examples of the acyl group include acetyl and benzoyl.

The alkoxy group includes a substituted alkoxy group and an unsubstituted alkoxy group. As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable. Examples of substituents include alkoxy groups, hydroxyl groups, and ionic hydrophilic groups. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group includes substituted aryloxy groups and unsubstituted aryloxy groups. As the aryloxy group, an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of substituents include alkoxy groups and ionic hydrophilic groups. Examples of the aryloxy group include phenoxy, p-methoxyphenoxy and o-methoxyphenoxy.

The acyloxy group includes a substituted acyloxy group and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 12 carbon atoms. Examples of substituents include ionic hydrophilic groups. Examples of acyloxy include acetoxy and benzoyloxy.

The carbamoyloxy group includes a substituted carbamoyloxy group and an unsubstituted carbamoyloxy group. Examples of substituents include alkyl groups. Examples of the carbamoyloxy group include N-methylcarbamoyloxy group.

The substituent of the amino group substituted with an alkyl group, an aryl group or a heterocyclic group may further have a substituent. Unsubstituted amino groups are not included. The alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms. Examples of substituents include ionic hydrophilic groups. Examples of alkylamino include methylamino and diethylamino. The arylamino group includes substituted arylamino groups and unsubstituted arylamino groups. As the arylamino group, an arylamino group having 6 to 12 carbon atoms is preferable. Examples of substituents include halogen atoms and ionic hydrophilic groups. Examples of the arylamino group include anilino and 2-chloroanilino.

The amido group includes amido groups having substituents. As the amido group, an amido group having 2 to 12 carbon atoms is preferable. Examples of substituents include ionic hydrophilic groups. Examples of amido include acetylamino, propionylamino, benzoylamino, N-phenylacetylamino and 3,5-disulfobenzoylamino.

The ureido group includes a substituted urea group and an unsubstituted urea group. As the ureido group, a urea group having 1 to 12 carbon atoms is preferable. Examples of substituents include alkyl and aryl. Examples of the ureido group include 3-methylureido, 3,3-dimethylureido and 3-phenylureido.

The sulfamoylamino group includes substituted sulfamoylamino groups and unsubstituted sulfamoylamino groups. Examples of substituents include alkyl groups. Examples of the sulfamoylamino group include N,N-dipropylsulfamoylamino group.

The alkoxycarbonylamino group includes substituted alkoxycarbonylamino groups and unsubstituted alkoxycarbonylamino groups. As the alkoxycarbonylamino group, an alkoxycarbonylamino group having 2 to 12 carbon atoms is preferable. Examples of substituents include ionic hydrophilic groups. Examples of alkoxycarbonylamino include ethoxycarbonylamino.

The aryloxycarbonylamino group includes substituted aryloxycarbonylamino groups and unsubstituted aryloxycarbonylamino groups. As the aryloxycarbonylamino group, an aryloxycarbonylamino group having 7 to 12 carbon atoms is preferable. Examples of substituents include ionic hydrophilic groups. Examples of the above-mentioned aryloxycarbonylamino group include phenoxycarbonylamino group.

The alkyl and arylsulfonylamino groups include substituted alkyl and arylsulfonylamino groups and unsubstituted alkyl and arylsulfonylamino groups. The sulfonylamino group is preferably a sulfonylamino group having 1 to 12 carbon atoms. Examples of substituents include ionic hydrophilic groups. Examples of the sulfonylamino group include methanesulfonylamino, 2-phenylmethanesulfonylamino, benzenesulfonylamino and 3-carboxybenzenesulfonylamino.

The alkyl, aryl and heterocyclic thio groups include substituted alkyl, aryl and heterocyclic thio groups and unsubstituted alkyl, aryl and heterocyclic thio groups. The alkyl group, aryl group and heterocyclic thio group preferably have 1 to 12 carbon atoms. Examples of substituents include ionic hydrophilic groups. Examples of alkyl, aryl and heterocyclic thio groups include methylthio, phenylthio, 2-pyridylthio.

Examples of the alkyl and arylsulfonyl groups include methylsulfonyl and benzenesulfonyl, respectively. Examples of the alkyl and arylsulfinyl groups include methanesulfinyl and phenylsulfinyl, respectively.

The sulfamoyl group includes substituted sulfamoyl groups and unsubstituted sulfamoyl groups. Examples of substituents include alkyl groups. Examples of the sulfamoyl group include dimethylsulfamoyl and bis-(2-hydroxyethyl)sulfamoyl.

Particularly preferable azo dyes in the present invention are represented by the following formula (3).

Formula (3)

[chemical 7]

In formula (3), Z ¹ represents an electron-withdrawing group having a Hammett substituent constant σρ value of 0.20 or more. Z ¹ is preferably an electron-withdrawing group having a σρ value of 0.30 to 1.0. Preferable specific substituents include electron-withdrawing substituents described below, among which, acyl groups having 2 to 12 carbon atoms, alkoxycarbonyl groups having 2 to 12 carbon atoms, nitro groups, cyano groups, and An alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and a haloalkyl group having 1 to 12 carbon atoms. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms, and a cyano group is most preferred.

R ¹ , R ² , R ⁵ , and R ⁶ have the same meaning as in the case of formula (2). R ³ and R ⁴ are each independently representing a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl group and an arylsulfonyl group or Sulfamoyl. Among them, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl group, and an arylsulfonyl group are preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable. Z ² represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Among them, Q is preferably a group containing non-metallic atom groups necessary for forming a 5- to 8-membered ring. The 5- to 8-membered ring may be substituted, and may be a saturated ring or have an unsaturated bond. Among them, an aromatic group and a heterocyclic group are particularly preferable. Preferable non-metal atoms include nitrogen atoms, oxygen atoms, sulfur atoms and carbon atoms. Specific examples of the 5- to 8-membered ring include benzene ring, cyclopentyl ring, cyclohexyl ring, cycloheptane ring, cyclooctyl ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, Triazine ring, imidazole ring, benzimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, oxane ring, sulfolane ring, thiane ring and the like.

Each group described in formula (3) may further have a substituent. When each of these groups further has a substituent, examples of the substituent include the substituents described in formula (2), the groups exemplified by G, R ¹ , and R ² , or ionic hydrophilic groups.

Here, regarding the substituent Z ₁ , the Hammett's substituent constant σρ value used in this specification will be described. Hammett's law is an empirical rule proposed by LP Hammett in 1935 to quantitatively study the influence of substituents on the reaction or equilibrium of benzene derivatives, and it is still widely recognized today. The substituent constants obtained in Hammett's rule include σρ value and σm value, and most of these values can be seen in general books, such as in JADean, "Lang's Chemistry Handbook", 12th edition, 1979 (McGraw -Hill) and "Chemical Field" Supplement, No. 122, pages 96-103, 1979 (Nan Guang Tang). It should be noted that in the present invention, the Hammett substituent constant σρ is used to define and illustrate each substituent, but this does not mean that it is limited to the substituents that can be seen in the above-mentioned books and have known values in the literature. Substituents whose values are not known in the literature but can be included in the range when measured by Hammett's law are included. In addition, substances other than benzene derivatives are also included in the formulas (2) and (3) of the present invention, and a σρ value irrespective of the substitution position is used as a scale showing the electronic effect of the substituent. In the present invention, the σρ value is used for this reason.

Examples of the electron-withdrawing group having a Hammett substituent constant σρ value of 0.60 or more include a cyano group, a nitro group, an alkylsulfonyl group (eg, methylsulfonyl group), and an arylsulfonyl group (eg, benzenesulfonyl group). As electron-withdrawing groups having a Hammett σρ value of 0.45 or more, in addition to the above, acyl groups (such as acetyl groups), alkoxycarbonyl groups (such as dodecyloxycarbonyl groups), aryloxycarbonyl groups, and (e.g. m-chlorophenoxycarbonyl), alkylsulfinyl (e.g. n-propylsulfinyl), arylsulfinyl (e.g. phenylsulfinyl), sulfamoyl (e.g. N-ethylsulfamoyl acyl, N,N-dimethylsulfamoyl), haloalkyl (eg trifluoromethyl).

As the electron-withdrawing group whose Hammett substituent constant σρ value is 0.30 or more, in addition to the above, acyloxy group (such as acetoxy group), carbamoyl group (such as N-ethylcarbamoyl group) can also be mentioned. , N,N-dibutylcarbamoyl), haloalkoxy (such as trifluoromethoxy), haloaryloxy (such as pentafluorophenoxy), sulfonyloxy (such as methylsulfonyloxy group), halogenated alkylthio group (such as difluoromethylthio group), aryl group substituted by two or more electron-withdrawing groups with a σρ value of 0.15 or higher (such as 2,4-dinitrophenyl, penta chlorophenyl) and heterocycles (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzoimidazolyl). Specific examples of the electron-withdrawing group having a σρ value of 0.20 or more include halogen atoms and the like in addition to the above.

As the azo dye represented by the above formula (2), particularly preferable combinations of substituents are as follows.

( ¹ ) R and ^R are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, an acyl group, more preferably a hydrogen atom, an aryl group, a heterocyclic group, a sulfonyl group, and most preferably a hydrogen atom, Aryl, heterocyclic. But R ⁵ and R ⁶ are not hydrogen atoms at the same time.

(2) G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an acyl group, or an amido group, more preferably a hydrogen atom, a halogen atom, an acyl group, or an amido group, and most preferably a hydrogen atom, an amino group, or an amido group.

(3) A is preferably a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, or a benzothiazole ring, more preferably a pyrazole ring or an isothiazole ring, and most preferably a pyrazole ring.

(4) B ¹ and B ² respectively represent -CR ¹ , -CR ² =, and these R ¹ and R ² are respectively preferably hydrogen atom, halogen atom, cyano group, carbamoyl group, carboxyl group, alkyl group, hydroxyl group, alkyl group An oxy group is more preferably a hydrogen atom, a cyano group, a carbamoyl group, or an alkyl group.

It should be noted that, for the preferred substituent combination of the compound shown in formula (2), preferably at least one of the various substituents is the compound of the above-mentioned preferred group, more preferably a plurality of substituents are the compound of the above-mentioned preferred group, Most preferred are compounds in which all substituents are the preferred groups mentioned above.

The compound represented by the above formula (2) can be produced by any method, for example, it can be produced by the following method.

(a) A compound represented by the following general formula (4) is reacted with a diazotization agent to form a diazonium salt.

(b) reacting the diazonium salt formed in the above step (a) with a coupling agent represented by the following general formula (5) to form a compound represented by the above general formula (2).

(c) In the presence of a base, react the compound formed in the above step (b) with an alkylating agent, an arylating agent, or a hybridizing agent (heteryl compound) to form a compound into which a substituent such as an alkyl group has been introduced. A compound represented by the above general formula (2).

Formula (4)

A-NH ₂

Formula (5)

[chemical 8]

(In the formula, A, G, B ¹ , B ² , R ⁵ , and R ⁶ have the same meaning as in the case of (2) above.)

Furthermore, when introducing a water-soluble group into the compound of the above formula (2), an electrophilic reaction is used. Examples of the electrophilic reaction include sulfonation, Mannich reaction, and Friedel-Crafts reaction, among which sulfonation is preferable.

Specific examples of compounds represented by formula (2) that can be preferably used in the present invention are given below.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

Next, the phthalocyanine compound represented by the general formula (I) which is a cyan dye used as a coloring agent in the aspect of the invention of the concept (B) will be described.

[chemical 9]

General formula (I)

In the above general formula (I), X ₁ , X ₂ , X ₃ and X ₄ each independently represent -SO-Z and -SO ₂ -Z, particularly preferably -SO ₂ -Z.

Z are independently substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl or substituted or unsubstituted Substituted heterocyclic groups, particularly preferably substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic groups, among which substituted alkyl groups, substituted aryl groups, and substituted heterocyclic groups are preferred, more preferably Substituted alkyl, substituted aryl, most preferably substituted alkyl.

The substituted or unsubstituted alkyl group represented by Z is preferably an alkyl group having 1 to 30 carbon atoms. Examples of substituents include the same substituents as Z, Y ₁ , Y ₂ , Y ₃ , and Y ₄ described later may further have substituents.

The substituted or unsubstituted cycloalkyl group represented by Z is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of substituents include the same substituents as Z, Y ₁ , Y ₂ , Y ₃ , and Y ₄ described later may further have substituents.

The substituted or unsubstituted alkenyl group represented by Z is preferably an alkenyl group having 2 to 30 carbon atoms. Examples of substituents include the same substituents as Z, Y ₁ , Y ₂ , Y ₃ , and Y ₄ described later may further have substituents.

The substituted or unsubstituted aralkyl group represented by Z is preferably an aralkyl group having 7 to 30 carbon atoms. Examples of substituents include the same substituents as Z, Y ₁ , Y ₂ , Y ₃ , and Y ₄ described later may further have substituents.

The substituted or unsubstituted aryl group represented by Z is preferably an aryl group having 6 to 30 carbon atoms. Examples of substituents include the same substituents as Z, Y ₁ , Y ₂ , Y ₃ , and Y ₄ described later may further have substituents.

The heterocyclic group represented by Z is preferably a 5-membered ring or a 6-membered ring, which may be further condensed. In addition, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. Hereinafter, the heterocyclic group represented by Z is exemplified in the form of a heterocyclic ring by omitting the substitution position, but the substitution position is not limited, for example, if it is pyridine, it can be substituted at the 2-position, 3-position, or 4-position. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxoline, pyrrole, indole, furan, benzofuran, thiophene, Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole Azole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazolidine, etc. Among them, the aromatic heterocyclic group is preferable, and if the preferred examples thereof are illustrated in the same manner as before, pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrrole, imidazole, benzimidazole, triazole, thiazole, benzo Thiazole, isothiazole, benzisothiazole, thiadiazole.

These groups may have substituents, and examples of the substituents include the same substituents as Z, Y ₁ , Y ₂ , Y ₃ and Y ₄ described later may further have substituents.

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently representing a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, Amino, alkylamino, alkoxy, aryloxy, amido, arylamino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl, alkoxy ylcarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonyl, aryloxycarbonylamino, imino, heterocyclic thio, phosphoryl, Acyl group, carboxyl group or sulfo group, each group may further have a substituent.

Among them, hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, sulfonamide group, carbamoyl group, alkoxycarbonyl group, carboxyl group and sulfo group are preferred, especially hydrogen atom, halogen atom, cyano group, carboxyl group and sulfo group, most preferably hydrogen atom.

When Y ₁ , Y ₂ , Y ₃ , Y ₄ and Z are groups that may further have substituents, they may further have the following substituents.

Halogen atom (such as chlorine atom, bromine atom); straight chain or branched alkyl group with 1 to 12 carbon atoms, aralkyl group with 7 to 18 carbon atoms, alkenyl group with 2 to 12 carbon atoms, 2 to 12 straight-chain or branched alkynyl groups, cycloalkyl groups with 3 to 12 carbon atoms that may have side chains, and cycloalkenyl groups with 3 to 12 carbon atoms that may have side chains (as specific examples of the above groups Examples include methyl, ethyl, propyl, isopropyl, tert-butyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl); aryl (such as phenyl, 4-tert-butylphenyl, 2,4-di-tert-pentylphenyl); heterocyclic groups (such as imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl , 2-pyrimidinyl, 2-benzothiazolyl); alkoxy (e.g. methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy); aryloxy (such as phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 3-tert-butyloxycarbonylphenoxy, 3-methoxycarbonylbenzene oxy); amido (e.g. acetamido, benzamide, 4-(3-tert-butyl-4-hydroxyphenoxy)butyramide); alkylamino (e.g. methylamino, butylamino, diethylamino , methylbutylamino); anilino (such as phenylamino, 2-chloroanilino); ureido (such as phenylureido, methylureido, N,N-dibutylureido); sulfamo Acylamino (e.g. N,N-dipropylsulfamoylamino); alkylthio (e.g. methylthio, octylthio, 2-phenoxyethylthio); arylthio (e.g. phenylthio group, 2-butoxy-5-tert-octylphenylthio group, 2-carboxyphenylthio group); alkoxycarbonylamino group (such as methoxycarbonylamino group); sulfonamide group (such as methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide); carbamoyl (such as N-ethylcarbamoyl, N,N-dibutylcarbamoyl); sulfamoyl (such as N-ethylsulfonyl, N,N -dipropylsulfamoyl, N,N-diethylsulfamoyl); sulfonyl (such as methylsulfonyl, octanesulfonyl, benzenesulfonyl, 4-methylbenzenesulfonyl); alkoxycarbonyl ( For example, methoxycarbonyl, butoxycarbonyl); heterooxyl (for example, 1-phenyltetrazol-5-oxo, 2-tetrahydropyrrolyloxy); azo (for example, phenylazo, 4 -methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propionylphenylazo); acyloxy (e.g. acetoxy); carbamoyloxy ( e.g. N-methylcarbamoyloxy, N-phenylcarbamoyloxy); silyloxy (e.g. trimethylsilyloxy, dibutylmethylsilyloxy); aryloxycarbonylamino (e.g. phenoxycarbonylamino), imino groups (e.g., N-succinimide, N-phenolimide); heterocyclic thio groups (e.g., 2-benzothiazylthio, 2,4-diphenyl Oxy-1,3,5-triazole-6-thio, 2-pyridinethio); sulfinyl (e.g. 3-phenoxypropylsulfinyl); phosphoryl (e.g. phenoxyphosphoryl, octane oxyphosphoryl, phenylphosphoryl); aryloxycarbonyl (e.g. phenoxycarbonyl); acyl (e.g. acetyl, 3-phenylpropanoyl, benzoyl); ionic hydrophilic groups (e.g. carboxyl, sulfo, quaternary ammonium, sulfonylsulfamoyl, and acylsulfamoyl); others include cyano, hydroxyl, nitro, amino, and the like. Among these substituents, hydroxyl, alkoxy, sulfamoyl, sulfonamide, amido, carbamoyl, cyano and ionic hydrophilic groups are preferred, among which hydroxyl, sulfamoyl, ionic hydrophilic group.

In the general formula (I), a ₁ to a ₄ and b ₁ to b ₄ respectively represent the number of substituents of X ₁ to X ₄ and Y ₁ to Y ₄ . a ₁ to a ₄ are each independently an integer of 0 to 4, and b ₁ to b ₄ are each independently an integer of 0 to 4. Here, when a ₁ to a ₄ and b ₁ to b ₄ are integers of 2 or more, a plurality of X ₁ to X ₄ and Y ₁ to Y ₄ may be the same or different, respectively.

a ₁ and b ₁ satisfy the relationship of a ₁ +b ₁ =4, each independently represents an integer from 0 to 4, particularly preferably a combination of a ₁ representing 1 or 2 and b ₁ representing 3 or 2, among which a ₁ is most preferred Represents 1, b ₁ represents a combination of 3.

a ₂ and b ₂ satisfy the relationship of a ₂ +b ₂ =4, each independently represents an integer from 0 to 4, particularly preferably a combination of a ₂ representing 1 or 2 and b ₂ representing 3 or 2, among which a ₂ is most preferred Represents 1, b ₂ represents a combination of 3.

a ₃ and b ₃ satisfy the relationship of a ₃ +b ₃ =4, each independently represents an integer of 0 to 4, particularly preferably a combination of 1 or 2 and b ₃ representing 3 or 2, _among which a ₃ is most preferred Represents 1, b ₃ represents a combination of 3.

a ₄ and b ₄ satisfy the relationship of a ₄ +b ₄ =4, each independently represents an integer from 0 to 4, particularly preferably a ₄ represents 1 or 2, b ₄ represents a combination of 3 or 2, and a ₄ is most preferred Represents 1, b ₄ represents a combination of 3.

M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide.

Preferable examples of M include Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh as metal elements other than hydrogen atoms. , Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, etc. As an oxide, VO, GeO, etc. are mentioned preferably. Preferable examples of hydroxides include Si(OH) ₂ , Cr(OH) ₂ , Sn(OH) ₂ and the like. Examples of halides include AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, ZrCl, and the like. Among them, Cu, Ni, Zn, Al, etc. are preferable, and Cu is most preferable.

In the phthalocyanine compound represented by the general formula (I), Pc (phthalocyanine ring) can form a dimer (such as Pc-M-L-M-Pc) or a trimer through L (2-valent linking group), and multiple The M present may be the same or different, respectively.

The divalent linking group represented by L is preferably oxy-O-, thio-S-, carbonyl-CO-, sulfonyl-SO ₂ -, imino-NH-, methylene-CH ₂ - and combinations of these groups formed by groups.

In the above general formula (I), the molecular weight of the phthalocyanine compound is preferably in the range of 750-3000, more preferably in the range of 995-2500, preferably in the range of 995-2000, most preferably in the range of 995-1800.

For the phthalocyanine compound represented by the general formula (I), when Pc (phthalocyanine ring) is formed into a dimer (such as Pc-M-L-M-Pc) or a trimer through L (2-valent linking group), the preferred molecular weight For example, a particularly preferable molecular weight is twice (in the case of a dimer) or three times (in the case of a trimer) the above-described particularly preferable molecular weight (in the range of 995 to 1800). Here, the preferred molecular weight of the aforementioned dimer or trimer is a value including the linker L.

Among the phthalocyanine compounds represented by general formula (I), at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y ₃ and Y ₄ is an ionic hydrophilic group or has An ionic hydrophilic group as a substituent.

The ionic hydrophilic groups as substituents include sulfo group (-SO ₃ ^- X ⁺ ), carboxyl group (-CO ₂ ^- X ⁺ ), quaternary ammonium group (-N ⁺ RR'R”X ^- ), acylsulfamo Acyl (-SO ₂ N ⁺ X ^- COR), sulfonylcarbamoyl (-CON ⁺ X ^- SO ₂ R), sulfonylsulfamoyl (-SO ₂ N ⁺ X ^- SO ₂ R), etc. Preferred is sulfonyl Group, carboxyl and quaternary ammonium group, sulfo group is particularly preferred. Sulfo group, carboxyl group, acylsulfamoyl group, sulfonylcarbamoyl group and sulfonylsulfamoyl group may be in the state of a salt, and examples of counterions that form salts include alkali metals ions (e.g. sodium, potassium, lithium), ammonium, organic cations (e.g. tetramethylguanidine), organic and/or inorganic anions (e.g. halides, methanesulfonate, benzenesulfonate). Should It should be noted that X in the above brackets represents a hydrogen atom or a counter ion, and R, R', R" represent a substituent.

Since the phthalocyanine compound represented by the general formula (I) has at least one ionic hydrophilic group or a group containing an ionic hydrophilic group as a substituent in one molecule, the dissolution in an aqueous medium Sexuality or dispersibility becomes better. From this point of view, the phthalocyanine compound represented by the general formula (I) preferably has at least two ionic hydrophilic groups in one molecule, and more preferably at least one of the plurality of ionic hydrophilic groups is sulfonic acid. groups, among which it is most preferable to have at least two sulfo groups in one molecule.

A particularly preferable compound as a phthalocyanine compound represented by the above general formula (I) is a compound having a combination of the following (1) to (6).

(1) X ₁ to X ₄ are each independently preferably -SO ₂ -Z.

(2) As far as Z is concerned, they are independently substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic group, among which substituted alkyl, substituted aryl, substituted Heterocyclyl, most preferably substituted alkyl.

(3) As far as Y ₁ to Y ₄ are concerned, they are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amido group, a urea group, a sulfonamide group, a carbamoyl group, A sulfamoyl group, an alkoxycarbonyl group, a carboxyl group and a sulfo group are particularly preferably a hydrogen atom, a halogen atom, a cyano group, a carboxyl group and a sulfo group, most preferably a hydrogen atom.

(4) a ₁ to a ₄ are each independently, preferably 1 or 2, particularly preferably 1. b ₁ -b ₄ are each independently, preferably 3 or 2, particularly preferably 3.

(5) M is preferably Cu, Ni, Zn or Al, among which Cu is most preferred.

(6) The molecular weight of the phthalocyanine compound is preferably in the range of 750 to 3000, more preferably in the range of 995 to 2500, especially preferably in the range of 995 to 2000, and most preferably in the range of 995 to 1800.

For the preferred substituent combination of the compound represented by the above general formula (I), preferably at least one of the various substituents is the compound of the above-mentioned preferred group, more preferably more substituents are the compound of the above-mentioned preferred group, most preferably all Compounds in which the substituents are the above-mentioned preferred groups.

Among the phthalocyanine compounds represented by the general formula (I), a phthalocyanine compound having a structure represented by the following general formula (III) is also preferable. Hereinafter, the phthalocyanine compound represented by the general formula (III) used in the present invention will be described in detail.

[chemical 10]

General formula (III)

In the above general formula (III), X ₂₁ , X ₂₂ , X ₂₃ and X ₂₄ each independently represent any one of -SO-Z and -SO ₂ -Z, particularly preferably -SO ₂ -Z.

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

Y ₂₁ to Y ₂₈ are each independent and have the same meaning as Y ₁ , Y ₂ , Y ₃ , and Y ₄ in the general formula (I), and preferred examples are also the same.

a ₂₁ to a ₂₄ satisfy 4 ≤ a ₂₁ + a ₂₂ + a ₂₃ + a ₂₄ ≤ 8, preferably satisfy 4 ≤ a ₂₁ + a ₂₂ + a ₂₃ + a ₂₄ ≤ 6, and each independently represent an integer of 1 or 2 . Particularly preferably a ₂₁ =a ₂₂ =a ₂₃ =a ₂₄ =1.

M is synonymous with M in the above general formula (I).

At least one of X ₂₁ , X ₂₂ , X ₂₃ , X ₂₄ , Y 21 , Y ₂₂ , Y ₂₃ , Y ₂₄ , Y ₂₅ , Y ₂₆ , Y ₂₇ , _and Y ₂₈ is an ionic hydrophilic group or has ionic properties A group in which a hydrophilic group is used as a substituent.

Examples of the ionic hydrophilic group are the same as the examples of X ₁ , X ₂ , X ₃ , and X ₄ in the general formula (I), and preferred examples are also the same.

Since the phthalocyanine compound represented by the general formula (III) has at least one ionic hydrophilic group or a group containing an ionic hydrophilic group as a substituent in one molecule, the dissolution in an aqueous medium Sex or dispersibility is good. From this point of view, the phthalocyanine compound represented by the general formula (III) is preferably a substance having at least two ionic hydrophilic groups in one molecule, more preferably at least one of a plurality of ionic hydrophilic groups. One is the substance of sulfo group, among which the substance with at least 2 sulfo groups in one molecule is most preferred.

In the general formula (III), the molecular weight of the phthalocyanine compound is preferably in the range of 750 to 3000, more preferably in the range of 995 to 2500, preferably in the range of 995 to 2000, most preferably in the range of 995 to 1800.

However, when the phthalocyanine compound represented by the general formula (III) of the present invention forms a dimer (for example, Pc-M-L-M-Pc) or a trimer through L (divalent linking group) via L (divalent linking group), Preferable molecular weight, for example, a particularly preferred molecular weight is twice (in the case of a dimer) or three times (in the case of a trimer) the above-described particularly preferred molecular weight (in the range of 995 to 1800). Here, the preferred molecular weight of the aforementioned dimer or trimer is a value including the linker L.

A particularly preferable compound as a phthalocyanine compound represented by the above general formula (III) is a compound having a combination of the following (1) to (6).

(1) X ₂₁ to X ₂₄ are each independently preferably -SO ₂ -Z.

(2) As far as Z is concerned, they are independently substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic group, among which substituted alkyl, substituted aryl, substituted Heterocyclyl, most preferably substituted alkyl.

(3) As far as Y ₂₁ to Y ₂₈ are concerned, they are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amido group, a urea group, a sulfonamide group, a carbamoyl group, A sulfamoyl group, an alkoxycarbonyl group, a carboxyl group and a sulfo group are particularly preferably a hydrogen atom, a halogen atom, a cyano group, a carboxyl group and a sulfo group, most preferably a hydrogen atom.

(4) a ₁₁ to a ₁₄ are each independently, preferably 1 or 2, particularly preferably a ₁₁ =a ₁₂ =a ₁₃ =a ₁₄ =1.

(5) M is preferably Cu, Ni, Zn or Al, among which Cu is most preferred.

(6) The molecular weight of the phthalocyanine compound is preferably in the range of 750 to 2500, more preferably in the range of 995 to 2500, especially preferably in the range of 995 to 2000, and most preferably in the range of 995 to 1800.

For the preferred substituent combination of the compound represented by the above-mentioned general formula (III), at least one of the various substituents is preferably the compound of the above-mentioned preferred group, more preferably more substituents are the compound of the above-mentioned preferred group, most preferably all Compounds in which the substituents are the above-mentioned preferred groups.

Among the phthalocyanine compounds represented by the general formula (III), a phthalocyanine compound having a structure represented by the following general formula (IV) is also preferable. Hereinafter, the phthalocyanine compound represented by the general formula (IV) used in the present invention will be described in detail.

[chemical 11]

General formula (IV)

Z ₁ , Z ₂ , Z ₃ , and Z ₄ in general formula (IV) are each independently synonymous with Z in general formula (I), and preferred examples are also the same.

q ₁ , q ₂ , q ₃ , and q ₄ are each independently an integer of 1 or 2, particularly preferably 2, and q ₁ =q ₂ =q ₃ =q ₄ =2 is most preferred.

a ₃₁ , a ₃₂ , a ₃₃ , and a ₃₄ each independently represent an integer of 1 or 2. 1 is particularly preferred, and a ₃₁ =a ₃₂ =a ₃₃ =a ₃₄ =1 is most preferred.

M is synonymous with M in the above general formula (I).

At least one of Z ₁ , Z ₂ , Z ₃ and Z ₄ has an ionic hydrophilic group as a substituent.

Examples of the ionic hydrophilic group are the same as the examples of Z in the above general formula (I), and preferred examples are also the same.

The molecular weight of the phthalocyanine compound is preferably in the range of 750 to 2500, more preferably in the range of 995 to 2500, particularly preferably in the range of 995 to 2000, most preferably in the range of 995 to 1800.

Among the compounds represented by the general formula (I) used in the present invention, compounds represented by the following general formula (II) are particularly preferred.

[chemical 12]

General formula (II)

In the formula, M has the same meaning as M in the general formula (I), and each of R ₁ to R ₄ independently represents -SO ₂ Z. Z has the same meaning as Z in the general formula (I), and the preferred examples are also the same. However, at least one of the four Zs has an ionic hydrophilic group as a substituent.

Among the above-mentioned compounds, it is more preferable that M in the general formula (II) is a copper element, and Z having an ionic hydrophilic group as a substituent is a compound of a sulfoalkyl group, and it is more preferable that the sulfo group is in the state of a salt or forms a salt. A compound in which the counter cation is a lithium cation.

The phthalocyanine compound represented by the following general formula (V) that can be used in the present invention is obtained by making the phthalocyanine compound represented by the following general formula (VI) and/or the dioxane represented by the following general formula (VII) Aminoisoindolin derivatives are synthesized by reacting with metal derivatives represented by M-(Y)d. It should be noted that Z and Z ₁ to Z ₄ are synonymous with Z in general formula (I), and M is synonymous with M in general formula (I). Y represents a monovalent or divalent ligand such as a halogen atom, an acetate anion, acetylacetonate, or oxygen, and d is an integer of 1 to 4. Examples of metal derivatives represented by M-(Y)d include Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt , Pb halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, complexes, etc. Specific examples include copper chloride, ketone bromide, ketone iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, ferric chloride, zinc chloride, bromine Zinc chloride, zinc iodide, zinc acetate, vanadium chloride, vanadium trichloride oxide, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, manganese acetylacetonate, manganese chloride, lead chloride, Lead acetate, indium chloride, titanium chloride, tin chloride, etc.

[chemical 13]

The compound represented by the above-mentioned general formula (V) obtained in this way is usually represented as R ₁ (SO ₂ -Z ₁ ), R ₂ (SO ₂ -Z ₂ ), R ₃ (SO ₂ -Z ₃ ), R ₄ (SO ₂ -Z ₄ ) A mixture of compounds represented by the following general formulas (a)-1 to (a) to 4, which are isomers at each substitution position.

Furthermore, when a dye is prepared using two or more types of general formula (VI) and/or general formula (VII) having different substituents, the compound represented by general formula (V) becomes a dye mixture having different types and positions of substituents.

[chemical 14]

General formula (a)-1 General formula (a)-2

General formula (a)-3 General formula (a)-4

Examples of the cyan-based dye used in the present invention include those described in JP-A-2002-249677, JP-A 2003-213167, JP-A 2003-213168, and JP-A 2004-2670. Compounds with equivalent structures are listed, but the compounds listed in the table below are particularly preferred. The compounds described in Table 7 and Table 8 can be synthesized by the methods described in the above publications or specifications. Of course, starting compounds, pigment intermediates and synthesis methods are not limited thereto.

[Table 7] m Z ₁ Z ₂ Z ₃ Z ₄ Compound A Cu -(CH ₂ ) ₃ SO ₃ Na -(CH ₂ ) ₃ SO ₃ Na -(CH ₂ ) ₃ SO ₃ Na -(CH ₂ ) ₃ SO ₃ Na Compound B Cu -(CH ₂ ) ₃ SO ₃ Li -(CH ₂ ) ₃ SO ₃ Li -(CH ₂ ) ₃ SO ₃ Li -(CH ₂ ) ₃ SO ₃ Li Compound C Cu -(CH ₂ ) ₃ CO ₂ K -(CH ₂ ) ₃ CO ₂ K -(CH ₂ ) ₃ CO ₂ K -(CH ₂ ) ₃ CO ₂ K Compound D Cu -CH ₂ CH(OH)CH ₂ SO ₃ Li -CH ₂ CH(OH)CH ₂ SO ₃ Li -CH ₂ CH(OH)CH ₂ SO ₃ Li -CH ₂ CH(OH)CH ₂ SO ₃ Li Compound E Cu -(CH ₂ ) ₂ CH(CH ₃ )SO ₃ Li -(CH ₂ ) ₂ CH(CH ₃ )SO ₃ Li -(CH ₂ ) ₂ CH(CH ₃ )SO ₃ Li -(OH ₂ ) ₂ CH(CH ₃ )SO ₃ Li

[Table 8]

m R ₁ n R ₂ m Compound F Cu -(CH ₂ ) ₃ SO ₃ Li 3 -(CH ₂ ) ₃ SO ₂ NHCH ₂ CH(OH)CH ₃ 1 Compound G Cu -(CH ₂ ) ₃ SO ₃ Li 2 -(CH ₂ ) ₃ SO ₂ NHCH ₂ CH(OH)OH ₃ 2 Compound H Cu -(CH ₂ ) ₃ SO ₃ Li 3 -(CH ₂ ) ₃ SO ₂ NHCH(CH ₃ )OH ₂ OH 1 Compound I Cu -(CH ₂ ) ₃ SO ₃ Li 2 -(CH ₂ ) ₃ SO ₂ NHCH(CH ₃ )CH ₂ OH 2 Compound J Cu -(CH ₂ ) ₃ SO ₃ Li 3 -(CH ₂ ) ₃ SO ₂ N(C ₂ H ₄ OH) ₂ 1 Compound K Cu -(CH ₂ ) ₃ SO ₃ Li 3 -(CH ₂ ) ₆ CO ₂ Li 1

In the table, the order of introduction position of each substituent of (SO ₂ R ₁ ) and (SO ₂ R ₂ ) is different.

(Represents the isomers represented by the above (a)-1 to (a)-4)

The values of m and n are the molar ratios of phthalonitrile derivatives used in the synthesis of phthalocyanine derivatives.

Hereinafter, the invention of (A) concept and the aspect similar to the invention of (B) concept are demonstrated.

The ink composition of the present invention contains at least one aromatic compound having a carboxyl group in order to reduce or eliminate the coppery floating phenomenon seen in solid printing and improve the moisture resistance of printed matter.

The aromatic compound having a carboxyl group used in the present invention may be any aromatic compound as long as it has at least one carboxyl group in its molecular structure, and is preferably a compound having at least one carboxyl group in the naphthalene skeleton. , more preferably a compound having a carboxyl group at the 2-position and having a naphthalene skeleton.

As a preferred form, it is possible to include an aromatic compound having a carboxyl group as an alkali metal salt and/or an ammonium salt, or simultaneously contain an alkali metal hydroxide and/or ammonia as a neutralizing agent (in this specification, a carboxyl group Alkali metal salts and ammonium salts of aromatic compounds are also included in aromatic compounds having a carboxyl group). Among the alkali metal salts, lithium salts are particularly preferable not only from the viewpoint of improving the copper light floating color resistance, but also from the viewpoint of eye blocking resistance in the coated state. From the standpoint of resistance to clogging in an uncoated state, sodium salts, potassium salts, or ammonium salts among alkali metal salts are preferable.

As the aromatic compound having a carboxyl group, specifically, 1-naphthoic acid, 2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthalene Formic acid, 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid, 3-methoxy-2-naphthoic acid, 3-ethoxy-2-naphthoic acid, 3-propane Oxy-2-naphthoic acid, 6-methoxy-2-naphthoic acid, 6-ethoxy-2-naphthoic acid, 6-propoxy-2-naphthoic acid and the like.

The content of these aromatic compounds having a carboxyl group is determined by the type of aromatic compound having a carboxyl group, the type of dye, the type of solvent component, etc., but relative to the total weight of the ink composition, it is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. range.

In the ink composition of the present invention, the content ratio of the dye and the aromatic compound having a carboxyl group is 1:0.2 to 1:10, more preferably 1:0.3 to 1.6. By making the ratio of aromatic compounds having carboxyl groups and/or salts thereof higher than 1:0.2, the resulting copper light floating phenomenon and the improvement effect of moisture resistance can be fully obtained. In addition, by making aromatic compounds having carboxyl groups The ratio of the substance and/or its salt is lower than 1:10, which can easily ensure the reliability of eye plugging and the like.

The ink composition of the present invention contains lithium ions. Lithium ions can be contained by adding an aromatic compound having a carboxyl group as a lithium salt, or by adding a lithium salt (or partial salt) as a colorant, or by adding a lithium compound such as lithium hydroxide as a neutralizing agent. contain.

In the invention of the concept (A), the concentration of lithium ions in the ink composition is preferably 0.001 to 0.1 mol per 100 g of the ink composition. In addition, in the invention of concept (B), the lithium ion content in the ink composition is preferably 1.2 times the number of moles of lithium ions relative to the number of moles of the sulfoalkyl group having an ionic hydrophilic group of the above-mentioned cyan dye. above, more preferably 1.4 to 3.0 times. In any concept of the invention, by the presence of lithium ions in the ink composition, the copper-flooding resistance effect of the aromatic compound having a carboxyl group is improved, and the reliability of the clogging resistance in the covered state is also improved. In addition, when lithium ions are bonded to -SO ₃ ^- groups in the colorant, the solubility of the colorant improves.

In terms of cations such as at least one of sodium ions, potassium ions, and ammonium ions selected from (A) the conceptual invention or (B) sodium ions and/or potassium ions in the conceptual invention, it is also the same as the above-mentioned lithium ion, and can be A fragrance composition having a carboxyl group or a coloring agent may be added as sodium salt, potassium salt, ammonium salt, and compounds such as sodium hydroxide, potassium hydroxide, and ammonium may be added separately.

The above-mentioned cations can prevent the ink nozzle from being damaged when the ink nozzle is placed under more severe use conditions (for example, when the power supply disappears during printing, the print head does not return to the original position, and the nozzle is placed in an uncovered state). The lithium salt of the carboxyl aromatic compound precipitates to cause clogging and ink droplet deflection, and can be used as an ink composition with further improved reliability such as clogging without deteriorating other characteristics. The reason for this is considered to be that when the above-mentioned cation is bonded to the ^-COO- group, the solubility is higher than when the lithium ion is bonded.

In the invention of the concept (A), the total molar ratio of at least one selected from sodium ions, potassium ions, and ammonium ions to lithium ions is preferably 8:1 to 1:1, more preferably 6:1 to 10: 9. In addition, in the invention of the concept (B), the content of sodium ions and/or potassium ions is preferably the total number of moles of sodium and potassium relative to the number of moles of the sulfoalkyl group having an ionic hydrophilic group of the above-mentioned cyan dye. It is 0.7 times or less, more preferably 0.1 to 0.6 times. By using it within this range, it is possible to prevent deposition of lithium salts without lowering the copper flooding resistance effect of the ink composition.

(A) In the ink composition of the concept invention, the total molar ratio of lithium ions, sodium ions, potassium ions and ammonium ions relative to the aromatic compound having a carboxyl group is preferably 1:5 to 10:8, more preferably 1: 4～1:1. By containing alkali metal ions in such a ratio, the clogging resistance under normal use conditions and more severe use conditions can be ensured at the same time, and the ink resistance of the parts of the ink cartridge can be maintained (prevention of parts from elution into the ink composition) wait).

(B) In the ink composition of the conceptual invention, the total number of moles of sodium and potassium is at least 0.3 times, more preferably 0.4 to 1.0 times, the number of moles of carboxyl groups of the aromatic composition having carboxyl groups. By containing sodium and/or potassium in such a ratio, the solubility of the aromatic compound having a carboxyl group can be improved, and the precipitation of a lithium salt can be prevented.

In order to stabilize and dissolve the specified amount of the dye and the aromatic compound having a carboxyl group and/or its salt, the pH (20° C.) of the ink composition is preferably 7.5 or higher. In addition, considering the material resistance of various parts that come into contact with the ink composition, the pH of the ink composition is preferably 10.0 or less. In order to better balance these matters, it is more preferable to adjust the pH of the ink composition to 8.0 to 9.5.

Especially in (B) concept invention, on the basis of ensuring such a pH, relative to the mole of the sulfoalkyl group having an ionic hydrophilic group of the above-mentioned cyan dye and the carboxyl group of the above-mentioned aromatic compound having a carboxyl group The total number, the sum of the moles of lithium ions, sodium ions, and potassium ions is preferably 0.8 to 1.2 times.

In addition, although there are cases where the sum of the moles of lithium ions, sodium ions, and potassium ions exceeds the above range on the basis of ensuring the pH (for example, adding NaCl, KCl, etc., it becomes 1.2 times or more), but the ions that are more than necessary are dissolved in the ink. When, the solubility of the dye tends to be reduced, which is not preferred.

If urea is further added to the ink composition of the present invention, the effect of preventing ink nozzle clogging and ink droplet bending under more severe usage conditions will be further enhanced. Urea also has an effect of preventing the precipitation of lithium salts of aromatic compounds having carboxyl groups. The urea concentration in the ink composition is preferably 1 to 6% by weight, more preferably 1.5 to 5.5% by weight. By using it within this range, generation of lithium salts can be effectively prevented without deteriorating the clogging resistance. In addition, by using it in combination with an aromatic compound having a carboxyl group, it is also possible to further improve the copper-color floating resistance.

The ink composition of the present invention may further contain a humectant selected from water-soluble organic solvents having a vapor pressure lower than pure water and/or sugars.

By containing a humectant, in the inkjet recording method, the evaporation of water can be suppressed and the ink can be moisturized. In addition, if it is a water-soluble organic solvent, the ejection stability can be improved, and the viscosity can be easily changed without changing the characteristics of the ink.

The water-soluble organic solvent refers to a medium capable of dissolving solutes, and is selected from water-soluble mediums that are organic and have a vapor pressure lower than that of water. Specifically, ethylene glycol, propylene glycol, butanediol, pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, glycerin, 1,2 , 6-hexanetriol, diethylene glycol, triethylene glycol, dipropylene glycol and other polyols, acetonylacetone and other ketones, γ-butyrolactone, triethyl phosphate and other esters, furfuryl alcohol, tetrahydrofurfuryl alcohol, Thiodiglycol, etc.

In addition, the sugars are preferably maltitol, sorbitol, gluconolactone, maltose, and the like.

The humectant is preferably added in an amount of 5 to 50% by weight, more preferably 5 to 30% by weight, and still more preferably 5 to 20% by weight based on the total amount of the ink composition. When it is 5% by weight or more, moisture retention can be obtained, and if it is 50% by weight or less, it is easy to adjust the viscosity for inkjet recording.

In addition, it is also preferable to contain a nitrogen-containing organic solvent as a solvent in the ink composition of the present invention. Examples of nitrogen-containing organic solvents include 1,3-dimethyl-2-imidazolinone, 2-pyrrolidone, N-methyl-2-pyrrolidone, and ε-caprolactone, among which 2- pyrrolidone. These solvents may be used alone or in combination of two or more.

The content thereof is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight. When the content is 0.5% by weight or more, the solubility of the colorant of the present invention can be improved by addition, and when the content is 10% by weight or less, the material resistance of various parts in contact with the ink composition will not be deteriorated.

In addition, it is preferable that the ink composition of the present invention contains a nonionic surfactant as an additive effective in maintaining the roundness of one point while obtaining rapid adhesion (penetration) of the ink.

Examples of the nonionic surfactant used in the present invention include acetylene glycol-based surfactants. Specific examples of acetylene glycol-based surfactants include SURFYNOL 465, SURFYNOL 104 (the above are manufactured by Air Products and Chemicals, Inc., trade name), OLFIN STG, OLFIN E1010 (the above are manufactured by Nissin Chemical Industry Co., Ltd., product name), etc. The added amount thereof is 0.1 to 5% by weight, preferably 0.5 to 2% by weight. Sufficient permeability can be obtained by making the addition amount 0.1 weight% or more. In addition, by making it 5% by weight or less, it is easy to prevent the occurrence of image bleeding.

And on the basis of nonionic surfactants, by adding glycol ethers as a penetration accelerator, the penetration can be further improved while reducing the boundary penetration between adjacent color inks during color printing, and can obtain Very sharp images.

Examples of glycol ethers used in the present invention include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monobutyl ether, and propylene glycol monobutyl ether. Butyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether, etc. The added amount thereof is 3 to 30% by weight, preferably 5 to 15% by weight. When the added amount is less than 3% by weight, the permeation prevention effect cannot be obtained. When it exceeds 30% by weight, not only image bleeding occurs, but also oily separation occurs, so these glycol ether-based dissolution aids are required, and the viscosity of the ink increases accordingly, making it difficult to eject from the inkjet head.

In the ink composition of the present invention, it is also possible to add pH regulators such as triethanolamine and alkali metal hydroxides, hydrotropes such as urea and its derivatives, water-soluble polymers such as sodium alginate, water-soluble resins, etc. Fluorinated surfactants, fungicides, rust inhibitors, etc.

The preparation method of the ink composition of the present invention includes, for example, a method in which components are fully mixed and dissolved, filtered under pressure through a membrane filter with a pore size of 0.8 μm, and then degassed with a vacuum pump.

Next, the recording method of the present invention using the ink composition described above will be described. In the recording method of the present invention, it is particularly preferable to use an inkjet recording method in which the ink composition is ejected as liquid droplets from micropores, and the liquid droplets are attached to a recording medium for recording. Of course, it can also be used in ordinary writing instruments, Recorders, pen plotters, etc.

As the inkjet recording method, any method known in the past can be used, especially in the method of using the vibration of the piezoelectric element to eject the liquid droplets (recording using the inkjet head that forms the liquid droplets by the mechanical deformation of the electrostrictive element). method) and a method using thermal energy can perform excellent image recording.

Next, the present invention will be specifically described by giving examples and comparative examples of the present invention.

It should be noted that the present invention is not limited by the following examples.

[Examples 1 to 11 and Comparative Examples 1 to 8]

The components were mixed and dissolved in the compounding ratio shown in Table 9, and pressure filtration was performed through a membrane filter with a pore size of 1 μm to prepare the respective ink compositions of Examples 1 to 11 and Comparative Examples 1 to 8. Each component of the ink composition shown in Table 9 represents the weight % of each component relative to the total amount of the ink composition. In addition, M dye 1 in Table 9 is a compound represented by following formula (6).

Formula (6)

[chemical 15]

(In formula (6), M represents NH ₄ or Na, NH ₄ : Na=1:1 (molar ratio).)

M dye 2 is a compound of dye 8 in Table 3, comparative dye 1 is C.I.Direct Red 227, and comparative dye 2 is C.I.Acid Red 249.

The number of moles of Li and the number of moles of Na+K+ _NH3 in this combination, the ratio of the number of moles of Li+Na+K+NH3 relative to the number of moles of carboxyl groups of 2-naphthoic acid, and the ratio of moles of Li+Na+K+ _NH3 to the number of carboxyl groups of 2-naphthoic acid, relative to Na+K+ _NH3 The Li mole ratio of Li+Na+K+ _NH The mole number, the weight ratio of 2-naphthoic acid relative to the coloring agent are shown in Table 10.

[Table 9] M dye 1 M dye 2 Comparative Dye 1 Compare Dye 2 2-naphthoic acid LIOH·H ₂ O NaOH NH ₃ urea glycerin Triethylene glycol monobutyl ether Triethylene glycol Triethanolamine OLFIN E10l0 water total Example 1 3.00 2.00 0.48 10.00 10.00 6.00 0.50 0.80 67.22 100.00 Example 2 3.00 3.00 0.72 10.00 10.00 5.00 0.50 0.80 66.98 100.00 Example 3 3.00 3.00 0.72 0.50 10.00 10.00 4.80 0.50 0.80 66.68 100.00 Example 4 3.00 3.00 0.72 8.00 10.00 10.00 1.50 0.50 0.80 62.48 100.00 Example 5 3.00 3.00 2.10 1.30 3.00 10.00 10.00 3.00 0.50 0.80 63.30 100.00 Example 6 3.00 5.00 0.50 3.00 10.00 10.00 1.00 0.50 0.80 66.20 100.00 Example 7 3.00 3.00 0.45 0.25 3.00 10.00 10.00 3.00 0.50 0.80 66.00 l00.00 Example 8 3.00 3.00 0.45 0.11 3.00 10.00 10.00 3.00 0.50 0.80 66.14 100.00 Example 9 3.00 3.00 0.10 3.00 10.00 10.00 3.00 0.50 0.80 66.60 100.00 Example 10 3.00 3.00 3.60 3.00 10.00 10.00 3.00 0.50 0.80 63.10 100.00 Example 11 3.00 3.00 0.72 3.00 10.00 10.00 3.00 0.50 0.80 65.98 100.00 Comparative example 1 3.00 10.00 10.00 8.00 0.50 0.80 67.70 100.00 Comparative example 2 3.00 10.00 10.00 8.00 0.50 0.80 67.70 100.00 Comparative example 3 3.00 10.00 10.00 8.00 0.50 0.80 67.70 100.00 Comparative example 4 3.00 10.00 10.00 8.00 0.50 0.80 67.70 100.00 Comparative Example 5 3.00 2.00 0.45 10.00 10.00 6.00 0.50 0.80 67.25 100.00 Comparative Example 6 3.00 3.00 0.70 10.00 10.00 5.00 0.50 0.80 67.00 100.00 Comparative Example 7 3.00 2.00 0.45 3.00 10.00 10.00 4.00 0.50 0.80 66.25 100.00 Comparative Example 8 3.00 3.00 0.70 3.00 10.00 10.00 3.00 0.50 0.80 66.00 100.00

The values in the table represent % by weight.

OLFIN E1010: Trade name, produced by Nissin Chemical Co., Ltd.

[Table 10] LI (moles) Na+K+NH ₃ (moles) Li+Na+K+NH ₃ (moles)/carboxyl group of 2-naphthoic acid (moles) Li(moles)/Na+K+NH ₃ (moles) Li+Na+K+NH ₃ (moles) 2-naphthoic acid/colorant (wt%) Example 1 0.011 0.009 1.787 1.228 0.021 0.667 Example 2 0.017 0.010 1.533 1.797 0.027 1.000 Example 3 0.017 0.010 1.533 1.797 0.027 1.000 Example 4 0.017 0.010 1.533 1.797 0.027 1.000 Example 5 0.050 0.042 5.286 1.190 0.092 1.000 Example 6 0.012 0.010 0.739 1.248 0.021 1.667 Example 7 0.011 0.016 1.522 0.679 0.027 1.000 Example 8 0.011 0.016 1.535 0.669 0.027 1.000 Example 9 0.002 0.010 0.685 0.250 0.012 1.000 Example 10 0.086 0.010 5.472 8.984 0.095 1.000 Example 11 0.017 0.010 1.533 1.797 0.027 1.000 Comparative example 1 0 0.009 - 0 0.009 0 Comparative example 2 0 0.010 - 0 0.010 0 Comparative example 3 - - - - - 0 Comparative example 4 - - - - - 0 Comparative Example 5 0 0.021 1.771 0 0.021 0.667 Comparative example 6 0 0.027 1.552 0 0.027 1.000 Comparative Example 7 0 0.021 1.771 0 0.021 0.667 Comparative Example 8 0 0.027 1.552 0 0.027 1.000

<Printing of recorded matter>

Using an inkjet printer Stylus Color 880 (trade name, produced by SEIKO EPSON Co., Ltd.), the ink compositions of Examples 1 to 10 and Comparative Examples 1 to 8 shown in Table 9 are filled in its dedicated ink cartridge (Magenta chamber), relative to An inkjet-only recording medium (PM photo paper; manufactured by SEIKO EPSON Co., Ltd., model: KA420PSK) was printed and evaluated as follows.

<Evaluation of light resistance>

Using ink cartridges filled with the ink compositions of Examples 1 and 2 and Comparative Examples 1 to 4, printing was performed by adjusting the coverage of each ink composition so that the OD value (absorbance) fell within the range of 0.9 to 1.1. After leaving it in a normal-temperature and normal-humidity environment out of direct sunlight for 1 day, the light resistance of the obtained recorded matter was evaluated under the following conditions.

Using a fluorescent lamp weather resistance tester SFT-II (manufactured by SUGA Testing Instrument Co., Ltd.), the recorded object was irradiated with an illumination intensity of 70,000 lux for 11 days under the conditions of 24° C. and 60% RH.

The OD value (absorbance) of the exposed sample was measured using a reflection densitometer (manufactured by "Spectrolino" Gretag). By substituting each measured value into the following formula, the optical density residual ratio after fading (residual absorbance; ROD) was obtained.

ROD(%)=(D _n /D ₀ )×100

(D _n : OD after irradiation test, D ₀ : OD before irradiation test)

A: ROD (%) 85% or more

B: ROD (%) 70% or more and less than 85%

C: ROD (%) 55% or more and less than 70%

D: ROD (%) is less than 55%

The evaluation results are shown in Table 11.

<Evaluation of gas resistance (ozone resistance)>

Using ink cartridges filled with the ink compositions of Examples 1 and 2 and Comparative Examples 1 to 4, printing was performed by adjusting the coverage of each ink composition so that the OD value (absorbance) fell within the range of 0.9 to 1.1. After leaving it in an environment of normal temperature and normal humidity where direct sunlight is not irradiated for 1 day, the ozone resistance of the obtained recorded matter was evaluated under the following conditions.

Using an ozone weathering tester OMS-H type (trade name, manufactured by SUGA Tester Co., Ltd.), the recorded material was exposed for 24 hours under the conditions of 24° C., 60% RH, and an ozone concentration of 10 ppm.

The OD value (absorbance) of the exposed sample was measured using a reflection densitometer (manufactured by "Spectrolino" Gretag). By substituting each measured value into the following formula, the optical density residual ratio after fading (residual absorbance; ROD) was obtained.

ROD(%)=(D _n /D ₀ )×100

(D _n : OD after irradiation test, D ₀ : OD before irradiation test)

A: ROD (%) 85% or more

B: ROD (%) 70% or more and less than 85%

C: ROD (%) 55% or more and less than 70%

D: ROD (%) is less than 55%

The evaluation results are shown in Table 11.

<Moisture resistance evaluation>

Using ink cartridges filled with the ink compositions of Examples 1 and 2 and Comparative Examples 1 to 4, characters and outline characters were printed under discharge conditions of 1.5 to 2.2 mg injection per square inch. After drying the obtained printed matter in an environment of 25°C and 40% RH for 24 hours, it was left to stand in an environment of 40°C and 85% RH for 3 days, and the bleeding of the dye (destruction of outline characters) was visually confirmed, and the following criteria were passed The moisture resistance was evaluated, and the results are shown in Table 11.

A: Bleeding out of the dye was hardly observed.

B: A level where there is some bleeding of the dye and the character outline is slightly damaged.

C: The level at which bleeding of the dye and destruction of the character outline were observed.

D: Bleeding of the dye is observed, and the characters are very thick, and the level where hollow characters spread over the entire body.

<Evaluation of eye blocking> (with cover)

The ink cartridges filled with the ink compositions of Examples 1 to 10 and Comparative Examples 5 to 8 were continuously printed for 10 minutes, and after confirming that all the nozzles were ejected normally, they were left for 4 weeks in an environment of 60° C. and 15% RH. After standing, the cleaning operation was repeated until all the nozzles ejected equally to the initial stage, and the ease of recovery was evaluated according to the following criteria. The results are shown in Table 12.

A: It returns to the same as the initial stage by 1 to 4 cleaning operations.

B: The same as the initial stage was restored by cleaning operations 5 to 8 times.

C: The same as the initial stage was restored by 9 to 12 cleaning operations.

D: There was no recovery even by the actual number of cleaning operations.

<Evaluation of eye blocking> (without cap)

(eye blockage recovery)

Use the ink cartridge filled with the ink composition of Examples 1 to 10 to print continuously for 10 minutes. After confirming that all nozzles are ejected normally, remove the recording head from the head cover with the ink cartridge installed. It was left for 1 week and 2 weeks in an environment of 40° C. and 20% RH. After being left to stand, the cleaning operation was repeated until all the nozzles ejected equally to the initial stage, and the ease of recovery was evaluated according to the following criteria, and the results are shown in Table 13.

A: It returns to the same as the initial stage by 1 to 4 cleaning operations.

B: The same as the initial stage was restored by cleaning operations 5 to 8 times.

C: The same as the initial stage was restored by 9 to 12 cleaning operations.

D: There was no recovery even by the actual number of cleaning operations.

(ink drop bending)

A solid pattern was printed at a coverage rate of 40% using the above-mentioned printer after recovery from plugging. Judgment was performed by visual inspection according to the following judgment criteria. The results are shown in Table 13.

A: The ground is covered, and there is no change from the initial stage.

B: There are some changes compared with the initial stage.

C: The ground is not covered, and there are many textures.

<Parts ink resistance>

10 g of polypropylene pellets (manufactured by Mitsui Chemicals, Inc., Mitsui Polypro ^™ J105G) were soaked in 20 g of each ink composition of Examples 1 to 10, and stored at 70° C. for 5 days and 10 days. After storage, it was left to stand at 5° C. for 3 days, and floating foreign matter was visually confirmed.

A: There is no floating foreign matter.

B: There is a small amount of floating foreign matter.

C: There are a lot of floating foreign substances.

The results are shown in Table 13.

[Table 11] Lightfastness Gas resistance Moisture resistance Example 1 B A B Example 2 A B B Comparative example 1 B A D. Comparative example 2 A B D. Comparative example 3 D. D. A Comparative example 4 D. D. D.

[Table 12]

Blockage resistance (with cover) result Example 1 A Example 2 A Example 3 A Example 4 C Example 5 B Example 6 C Example 7 C Example 8 C Example 9 C Example 10 B Example 11 B Comparative Example 5 D. Comparative Example 6 D. Comparative Example 7 D. Comparative Example 8 D.

[Table 13] Blocking resistance (without cover) Part Ink Resistance restorative ink drop bend 1 week 2 weeks 1 week 2 weeks 5 days 10 days Example 1 A A B C A A Example 2 A A B C A A Example 3 A A B C A A Example 4 B C A A A B Example 5 A A A A B C Example 6 A B A B A A Example 7 A B A A A A Example 8 A B A A A A Example 9 B C A B A A Example 10 A A A A A C Example 11 A A A A B A

In the image fastness evaluation shown in Table 11, Comparative Example 3 using Comparative Dye 1 was inferior in light fastness and gas resistance, and Comparative Example 4 using Comparative Dye 2 was inferior in all items. In addition, the ink compositions of Examples 1 and 2 had improved moisture resistance compared to Comparative Examples 1 and 2 in which 2-naphthoic acid was not used, using the same dye as in Examples.

In the clogging resistance (with a cover) shown in Table 12, Comparative Examples 5 to 8 not containing lithium were all evaluated as D, while Examples 1 to 11 were not evaluated as D. It can be seen that the addition of urea degrades some characteristics, so the addition amount is preferably within 6% by weight (compared to Example 4 of Example 11). When the amount of alkali metal ions is within a preferable range relative to 2-naphthoic acid, the characteristics are further improved (Example 11 compared to Examples 6 and 9). In addition, when the number of moles of lithium with respect to the total amount of sodium, potassium, and ammonium is in a preferable range, the characteristics are further improved (compared to Example 11 of Examples 7 to 9).

In Examples 1 to 11, there was no evaluation of D in the recovery properties of eye blocking resistance (without cap) shown in Table 13, and all of them were A or B in the evaluation within one week. When the amount of alkali metal ions is in a preferable range with respect to 2-naphthoic acid, the characteristics are further improved (Example 11 compared to Examples 6 and 9). In addition, when the number of moles of lithium with respect to the total amount of sodium, potassium, and ammonium is in a preferable range, the characteristics are further improved (compared to Example 11 of Examples 7 to 9). Ink drop deflection was also all A or B in the evaluation within one week. Compared with the case where urea was not contained (Examples 1 and 2) or the added amount was not in the preferable range (Example 3), when the added amount of urea was in the preferable range, the characteristics were further improved (Examples 5 to 11). In addition, when the amount of alkali metal ions is in a preferable range with respect to 2-naphthoic acid, the characteristics are further improved (Example 11 compared to Examples 6 and 9).

Regarding ink resistance of parts, when the amount of alkali metal ions is in a preferable range with respect to 2-naphthoic acid, the characteristics are further improved (Examples 1 to 4, 7, 8, and 11 relative to Examples 5 and 10). The floating foreign matter was collected by filtration, and when confirmed by FT-IR, it was an alkali metal stearate. It is considered that the stearic acid-based compound contained in the polypropylene was eluted because the inks of Examples 5 and 10 had a high pH.

[Examples 12-21 and Comparative Examples 9-15]

The components were mixed and dissolved in the compounding ratio shown in Table 14, and filtered under pressure with a membrane filter having a pore size of 1 μm to prepare the respective ink compositions of Examples 12 to 21 and Comparative Examples 9 to 15. Each component of the ink composition shown in Table 14 represents the weight % of each component relative to the total amount of the ink composition. It should be noted that, in the composition of Comparative Example 12, 2-naphthoic acid was not completely dissolved, and an ink composition usable for evaluation could not be obtained. In addition, in Comparative Example 13, the pH of the ink was 11.8, and there was a problem with the ink resistance of the printed part, so no evaluation was performed.

The number of moles of lithium ions and the number of moles of sodium ions + potassium ions to the number of moles of sulfoalkyl groups having ionic hydrophilic groups in the cyan dye in this composition, the number of moles of sodium to the number of carboxyl groups of 2-naphthoic acid Table 15 shows the ratio of the number of moles of ions+potassium ions, etc.

[Table 14] C dye compare dyes 2-naphthoic acid LiOH H ₂ O NaOH urea glycerin Triethylene glycol monobutyl ether Triethylene glycol Triethanolamine OLFIN E1010 water total Example 1 4.700 2.000 0.225 0.215 10.000 10.000 4.000 0.500 0.800 67.560 100.000 Example 2 4.700 2.000 0.225 0.2l5 0.500 10.000 10.000 3.800 0.500 0.800 67.260 100.000 Example 3 4.700 2.000 0.225 0.215 7.000 10.000 10.000 2.000 0.500 0.800 62.560 100.000 Example 4 4.700 2.000 0.050 0.380 10.000 10.000 4.000 0.500 0.800 67.570 100.000 Example 5 4.700 2.000 0.325 0.120 10.000 10.000 4.000 0.500 0.800 67.555 100.000 Example 6 4.700 2.000 0.430 4.000 10.000 10.000 2.800 0.500 0.800 64.770 100.000 Example 7 4.700 2.000 0.050 0.380 4.000 10.000 l0.000 2.800 0.500 0.800 64.770 100.000 Example 8 4.700 2.000 0.365 0.080 4.000 10.000 10.000 2.800 0.500 0.800 64.755 100.000 Example 9 4.700 2.000 0.325 0.120 4.000 10.000 10.000 2.800 0.500 0.800 64.755 100.000 Example 10 4.700 2.000 0.225 0.215 4.000 10.000 10.000 2.800 0.500 0.800 64.760 100.000 Comparative example 1 4.700 10.000 10.000 5.800 0.500 0.800 68.200 100.000 Comparative example 2 4.700 10.000 10.000 5.800 0.500 0.800 68.200 l00.000 Comparative example 3 4.700 4.000 10.000 10.000 4.600 0.500 0.800 65.400 100.000 Comparative example 4 4.700 2.000 10.000 10.000 4.000 0.500 0.800 68.000 100.000 Comparative Example 5 4.700 0.200 10.000 10.000 5.800 0.500 0.800 68.000 I00.000 Comparative Example 6 4.700 2.000 0.450 10.000 10.000 4.000 0.500 0.800 67.550 100.000 Comparative Example 7 4.700 2.000 0.450 4.000 10.000 10.000 2.800 0.500 0.800 64.750 l00.000

C Dye: Compound F

Compare Dyes: C.I. Direct Basket 199

OLFIN E1010: Trade name (manufactured by Nissin Chemical Industry Co., Ltd.)

[Table 15] Li (moles)/sulfoalkyl ( ) moles Na+K(moles)/sulfoalkyl(·)(moles) Na+K (moles)/carboxyl (moles) Dye/2-naphthoic acid (weight ratio) Alkali metal (moles)/sulfoalkyl ( ) + carboxyl (moles) Example 1 1.53 0.53 0.46 2.35 0.96 Example 2 1.53 0.53 0.46 2.35 0.96 Example 3 1.53 0.53 0.46 2.35 0.96 Example 4 1.12 0.94 0.82 2.35 0.96 Example 5 1.77 0.94 0.26 2.35 0.96 Example 6 1.00 1.06 0.93 2.35 0.96 Example 7 1.12 0.94 0.82 2.35 0.96 Example 8 1.86 0.20 0.17 2.35 0.96 Example 9 1.77 0.30 0.26 2.35 0.96 Example 10 1.53 0.53 0.46 2.35 0.96 Comparative example 1 - - - - - Comparative example 2 1.00 0 - - 1.00 Comparative example 3 1.00 0 - - 1.00 Comparative example 4 1.00 0 0 2.35 0.47 Comparative Example 5 1.47 0 - - 1.47 Comparative Example 6 2.06 0 0 2.35 0.96 Comparative Example 7 2.06 0 0 2.35 0.96

(·) Sulfonyl group: a sulfoalkyl group having an ionic hydrophilic group

<Printing of recorded matter>

Using an inkjet printer Stylus Color 880 (manufactured by SEIKO EPSON Co., Ltd.), the ink compositions of the above-mentioned Examples 12 to 21 and Comparative Examples 9 to 11, 14, and 15 are filled in its dedicated ink cartridge (Cyan chamber). A recording medium (PM photo paper; manufactured by SEIKO EPSON Co., Ltd., model; KA420PSK) was printed as follows and evaluated.

<Evaluation of Ozone Resistance>

Using ink cartridges filled with the ink compositions of Example 12 and Comparative Example 9, printing was performed by adjusting the coverage of each ink composition so that the OD value (absorbance) fell within the range of 0.9 to 1.1. After leaving it in an environment of normal temperature and normal humidity where direct sunlight is not irradiated for 1 day, the ozone resistance of the obtained recorded matter was evaluated under the following conditions.

The recorded material was exposed for 12 hours under the conditions of 24°C, 60% RH, and an ozone concentration of 10 ppm using an ozone weathering tester OMS-H type (trade name, manufactured by SUGA Tester Co., Ltd.).

The OD value (absorbance) of the exposed sample was measured using a reflection densitometer (manufactured by "Spectrolino" Gretag). By substituting each measured value into the following formula, the optical density residual ratio after fading (residual absorbance; ROD) was obtained.

ROD(%)=(D _n /D ₀ )×100

(D _n : OD after irradiation test, D ₀ : OD before irradiation test)

A: ROD (%) 85% or more

B: ROD (%) 70% or more and less than 85%

C: ROD (%) 55% or more and less than 70%

D: ROD (%) is less than 55%

As a result, the ink composition of Example 12 was evaluated as A, and the ink composition of Comparative Example 9 was evaluated as D.

<Evaluation of Copper Floating Color>

Using ink cartridges filled with the ink compositions of Examples 12 to 21 and Comparative Examples 10, 11, 14, and 15, image blocks divided into 32 parts relative to the maximum ink injection amount were printed in an environment of 32° C. and 65% RH (32: maximum, 0: not printed). Visually judge the degree of depth of floating color of copper light. The results are shown in Table 16.

<Evaluation of eye blocking> (with cover)

Use ink cartridges filled with the ink compositions of Examples 12 to 21 and Comparative Examples 10, 11, 14, and 15 to print continuously for 10 minutes, and after confirming that all nozzles are ejected normally, leave them in an environment of 60°C and 15%RH 3 weeks. After standing, the cleaning operation was repeated until all the nozzles ejected equally to the initial stage, and the ease of recovery was evaluated according to the following criteria. The results are shown in Table 16.

A: It returns to the same as the initial stage by 1 to 4 cleaning operations.

B: The same as the initial stage was restored by cleaning operations 5 to 8 times.

C: The same as the initial stage was restored by 9 to 12 cleaning operations.

D: There was no recovery even by the actual number of cleaning operations.

<Evaluation of eye blocking> (without cap)

(eye block recovery)

Use ink cartridges filled with the ink compositions of Examples 12 to 21 and Comparative Examples 10, 11, 14, and 15 to print continuously for 10 minutes. After confirming that all nozzles are ejected normally, restart the recording head with the ink cartridges installed. The lid was removed, and it was left to stand under the environment of 40 degreeC and 20%RH in this state for 1 week and 2 weeks. After standing, the cleaning operation was repeated until all the nozzles ejected equally to the initial stage, and the ease of recovery was evaluated according to the following criteria. The results are shown in Table 16.

A: It returns to the same as the initial stage by 1 to 4 cleaning operations.

B: The same as the initial stage was restored by cleaning operations 5 to 8 times.

C: The same as the initial stage was restored by 9 to 12 cleaning operations.

D: There was no recovery even by the actual number of cleaning operations.

(ink drop bending)

A solid pattern was printed at a coverage rate of 40% using the above-mentioned printer after recovery from plugging. Judgment was performed by visual inspection according to the following judgment criteria. The results are shown in Table 16.

A: The ground is covered, and there is no change from the initial stage.

B: There are some changes compared with the initial stage.

C: The ground is not covered, and there are many textures.

[Table 16] Copper light floating color resistance Anti-clogging eye (with cover) Blocking resistance (without cover) restorative ink drop bend 1 week 2 weeks 1 week 2 weeks Example 1 twenty two A A A A B Example 2 twenty four A A A A B Example 3 32 C C C A A Example 4 20 B A A A B Example 5 twenty three A B B A C Example 6 25 C B B A A Example 7 26 C B B A A Example 8 32 B C C A B Example 9 29 B C C A B Example 10 28 B B B A A Comparative example 2 9 A A A A A Comparative example 3 13 B B B A A Comparative Example 6 25 A B B C C Comparative Example 7 30 B C C B C

The anti-copper floating color performance was improved by using 2-naphthoic acid (Comparative Example 14 relative to Comparative Example 10), and was further improved by adding urea (Examples 13, 14, 17-21). In this case, the effect is greater when the urea content is 1% by weight or more of the ink composition. In addition, the number of moles of lithium is 1.2 times or more with respect to the number of moles of the sulfoalkyl group having an ionic hydrophilic group of the cyan dye, and the total number of moles of sodium and potassium is 0.7 times or less. Compared with lithium ions and sodium ions or potassium ions, but not in the preferred range, the copper light floating color resistance is high (compared to Example 12 of Example 15, and Example 21 compared to Examples 17 and 18).

In terms of eye blocking resistance (covered), the number of moles of lithium is 1.2 times or more with respect to the number of moles of sulfoalkyl groups having ionic hydrophilic groups of cyan dyes, and the moles of sodium and potassium The sum of the numbers is 0.7 times or less and compared with those containing lithium ions and sodium ions or potassium ions, but not in the preferred range, performance also improves (relative to embodiment 12 of embodiment 15, relative to embodiment 17, 18 Example 21). In addition, when the content of urea was 6% by weight or less, the reduction in eye blocking resistance due to urea was small (Example 13 compared to Example 14).

In terms of recovery from clogging resistance (without cap) and ink drop bending performance, it was improved by using NaOH. When the urea content is 6% by weight or less, the reduction in recovery caused by urea is small (compared to Example 13 and 21 of Example 14), and if it is more than 1% by weight, the bending of ink droplets can be reduced (compared to Example 13 Example 21). In addition, relative to the molar number of the carboxyl of 2-naphthoic acid, the molar sum of sodium and potassium is more effective than 0.3 times (relative to embodiment 12 of embodiment 16, relative to the embodiment of embodiment 19,20) twenty one).

Claims (22)

1. ink composite, said composition is characterized in that for containing water, tinting material at least and having the ink composite that the aromatics of carboxyl forms, contains at least a kind and lithium ion being selected from sodium ion, potassium ion and the ammonium ion.

2. ink composite, said composition is characterized in that for containing the cyan based dye shown in water, the following general formula (I) at least and having the ink composite that the aromatics of carboxyl forms, and contain lithium ion, sodium ion and/or potassium ion,

[changing 1]

General formula (I)

In the general formula (I), X ₁, X ₂, X ₃And X ₄Independent separately, expression-SO-Z and-SO ₂Any of-Z; Here, Z is independent separately, expression replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted thiazolinyl, replacement or unsubstituted aralkyl, replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic;

Y ₁, Y ₂, Y ₃And Y ₄Independent separately, the expression hydrogen atom, halogen atom, alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl, heterocyclic radical, cyano group, hydroxyl, nitro, amino, alkylamino, alkoxyl group, aryloxy, amide group, virtue is amino, urea groups, sulfamyl amino, alkylthio, arylthio, alkoxycarbonyl amino, sulfoamido, formamyl, alkoxy carbonyl, heterocyclic oxy group, azo-group, acyloxy, carbamoyloxy, siloxy-, aryloxycarbonyl, aryloxycarbonyl amino, imido grpup, the heterocycle sulfenyl, phosphoryl, acyl group or ionic hydrophilic radical, each group can also further have substituting group;

a ₁～a ₄And b ₁～b ₄Represent X respectively ₁～X ₂And Y ₁～Y ₄The replacement radix; a ₁～a ₄Separately independently, be 0～4 integer, be not 0 simultaneously; b ₁～b ₄Independent separately, the integer of expression 0～4;

M represents hydrogen atom, metallic element or its oxide compound, oxyhydroxide or halogenide;

But X ₁, X ₂, X ₃, X ₄, Y ₁, Y ₂, Y ₃And Y ₄At least 1 be ionic hydrophilic radical or have ionic hydrophilic radical as substituent group.

3. ink composite as claimed in claim 2 is characterized in that, the cyan based dye shown in the above-mentioned general formula (I) is represented by following general formula (II);

[changing 2]

General formula (II)

In the general formula (H), synonym in M and the general formula (I), R ₁～R ₄Expression-SO independently of one another ₂Z; Synonym in Z and the general formula (I); But at least 1 among 4 Z has ionic hydrophilic radical as substituting group.

4. ink composite as claimed in claim 3, the M of wherein said cyan based dye in above-mentioned general formula (II) is copper, the Z with ionic hydrophilic radical is a sulfoalkyl.

5. ink composite as claimed in claim 4, the counter cation of wherein said sulfoalkyl are lithium cation.

6. as each the described ink composite in the claim 1～5, it is characterized in that, also contain urea.

7. ink composite as claimed in claim 6 is characterized in that, contains the described urea of 1～6 weight % of ink composite.

8. as each the described ink composite in the claim 1,6,7, it is characterized in that with respect to described aromatics with carboxyl, at least a kind of total mol ratio with lithium ion that is selected from sodium ion, potassium ion and ammonium ion is 1: 5～10: 8.

9. ink composite as claimed in claim 8 is characterized in that, is selected from described lithium from being 8: 1～1: 1 in the mol ratio with at least a kind of sodium ion, potassium ion and ammonium ion.

10. as each the described ink composite in the claim 2～7, it is characterized in that, mole number with respect to the sulfoalkyl with ionic hydrophilic radical of described cyan based dye, the mole number of lithium ion is more than 1.2 times, and the total mole number of sodium ion and potassium ion is below 0.7 times.

11. each the described ink composite as in the claim 2～7,10 is characterized in that, with respect to described carboxyl mole number with aromatics of carboxyl, the total mole number of sodium ion and potassium ion is more than 0.3 times.

12. as each the described ink composite in the claim 2～7,10～11, it is characterized in that, with respect to the summation of the carboxyl mole number of the mole number of the sulfoalkyl with ionic hydrophilic radical of described cyan based dye and described aromatics with carboxyl, the total mole number of lithium ion, sodium ion, potassium ion is 0.8 times～1.2 times.

13. each the described ink composite as in the claim 1～12 is characterized in that, described aromatics with carboxyl is the aromatics with 1 carboxyl.

14. each the described ink composite as in the claim 1～13 is characterized in that, described aromatics with carboxyl is the compound with naphthalene skeleton.

15. ink composite as claimed in claim 14, wherein said compound with naphthalene skeleton is at 2 compounds with carboxyl.

16. ink composite as claimed in claim 15, the compound that wherein saidly have carboxyl at 2, has a naphthalene skeleton are at least a kind of 1-hydroxyl-2-naphthoic acid, 2-naphthoic acid, 3-hydroxyl-2-naphthoic acid, 6-hydroxyl-2-naphthoic acid, 3-methoxyl group-2-naphthoic acid, 6-methoxyl group-2-naphthoic acid, 6-oxyethyl group-2-naphthoic acid, 6-propoxy--2-naphthoic acid.

17., wherein, contain the described aromatics of 0.1～10 weight % with respect to the ink composite total amount with carboxyl as each the described ink composite in the claim 1～16.

18. as each the described ink composite in the claim 1～17, wherein, containing of described tinting material that comprises described cyan based dye and described aromatics with carboxyl proportionally counted 1: 0.2～1: 10 scope with weight ratio.

19. as each the described ink composite in the claim 1～18, wherein, said composition is used in ink jet recording method.

20. ink composite as claimed in claim 19, wherein said ink jet recording method are to use the mechanical deformation that utilizes electrostriction element and the recording method that forms the ink gun of droplets of ink.

21. ink jet recording method, this recording method for the ejection ink composite drop, make the ink jet recording method of this drop attached to the enterprising line item of recording medium, it is characterized in that, use each described ink composite of claim 1～20 as ink composite.

22. a record thing is characterized in that, uses each described ink composite of claim 1～20 to come record, perhaps comes record by the described recording method of claim 21.