JP2002121431A - Recording solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording solution capable of providing a clear magenta- based, cyanic or dark black-based printed matter even in the case of recording on a plain paper for ink-jet recording, having excellent printing density, light resistance, weather resistance (environmental gas resistance) and preservation stability. SOLUTION: This recording solution comprises an aqueous medium and at least one kind of a coloring matter selected from metal complex coloring matters formed from salts of a compound represented by general formula (1) in a free acid form, a compound represented by general formula (2), a compound represented by general formula (3) or a compound represented by general formula (4) and Cu, Co, Ni or Fe.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording liquid. More specifically, the present invention relates to a recording liquid suitable for inkjet.

[0002]

2. Description of the Related Art A recording method using an ink jet system has been widely used. A water-soluble dye or pigment is used as a colorant for the recording liquid used in this method. Pigments are excellent in durability, but they are dull in color tone, and there is concern about dispersion stability or ejection stability. The water-soluble dye has a vivid color tone, but does not have sufficient durability, especially light resistance and weather resistance. For this reason, various water-soluble dyes have been proposed. In particular, azo-based metal complex dyes are said to have high durability. For example, JP-A-56-155,263, JP-A-57-30,773, and JP-A-59-193,962.
JP-A-63-46260, JP-A-3-97,7
A number of patents have been proposed, such as No. 72, but have not yet been able to adequately satisfy market requirements.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a recording liquid for forming an image having a high density of a recorded image, excellent color tone, and excellent weather resistance and light resistance for ink jet recording. .

[0004]

Means for Solving the Problems The present inventors have found that when an azo metal complex dye having a specific structure is used among the azo metal complex dyes proposed so far, the image density, color tone and durability can be simultaneously improved. We have found that we have achieved the present invention. That is, the gist of the present invention is that the form of the free acid is a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), or a compound represented by the following general formula (4) And a compound represented by
It is present in a recording liquid containing at least one dye selected from metal complex dyes formed from salts of Co, Ni or Fe.

[0005]

Embedded image [Wherein A or B each independently represents a 2-hydroxy-phenyl group which may have a substituent, a 2-carboxy-phenyl group which may have a substituent or 4,
X represents a 5-dicyano-2-imidazolyl group, X represents a benzoyl group or a benzotriazolyl group which may be substituted with a hydroxy group, an alkoxy group or a sulfonic acid group; P represents a hydrogen atom or an alkyl group;
a, b and d each represent 0 or 1. ]

[0006]

Embedded image [In the formula, D represents a 2-hydroxy-phenyl group which may have a substituent, a 2-carboxy-phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group; Represents a phenyl group which may be substituted with a hydrogen atom or a carboxylic acid group, a sulfonic acid group or a nitro group, and E represents a substituted phenyl group, or a substituted pyridine group, or a substituted hydroxypyrazolyl group, or G represents a hydrogen atom or an alkyl group or an optionally substituted phenyl group, Y represents a hydroxy group or an amino group, and e, f, g, and h each represent a 4,5-dicyano-2-imidazolyl group. Represents 0 or 1. However, when the NH-Q group is at the 7-position when the OH group is at the 1-position, D is a substituted 2-hydroxy-phenyl group containing no nitro group, and may have a substituent. Represents a carboxy-phenyl group or a 4,5-dicyano-2-imidazolyl group. Also e
+ G represents 0 or 1. ]

[0007]

Embedded image [In the formula, J represents a 2-hydroxy-phenyl group which may have a substituent, a 2-carboxy-phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group, K represents an optionally substituted phenyl group or a 4,5-dicyano-2-imidazolyl group, Z represents a linking group, and l and m represent 0 or 1. ]

[0008]

Embedded image [In the formula, L represents a hydrogen atom or a phenyl group which may be substituted with a carboxy group, a sulfoxy group or a nitro group, and M represents an alkyl group, an alkoxy group, a halogen atom, a nitro group, a hydroxy group, Represents a good amino group, a phenyl group which may be substituted with a carboxylic acid group or a sulfonic acid group, or a substituted pyridine group, or a substituted hydroxypyrazolyl group; W represents a hydroxy group or an amino group; Represents 0 or 1. ]

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The dye used in the present invention includes a compound having a free acid form represented by the general formula (1), a compound represented by the general formula (2), a compound represented by the general formula (3), It is selected from metal complex dyes formed from the compound represented by (4) and a salt of Cu, Co, Ni or Fe.

In the general formula (1), in the 2-hydroxy-phenyl group represented by A and B, the substituent is a halogen atom such as a chlorine atom or a bromine atom or an alkyl group such as a methyl group or an ethyl group. Or an acylamino group such as a sulfonamide group, a nitro group, or an acetylamino group, or a triazinylamino group such as a 4-amino-6-hydroxy-triazinylamino group, a carboxylic acid group, or a sulfonic acid group. Can be

In the general formula (1), in the 2-carboxy-phenyl group represented by A or B, examples of the substituent include a chlorine atom, a nitro group, a carboxy group and a sulfoxy group.

In the general formula (1), examples of the group represented by P include a hydrogen atom or an alkyl group such as a methyl group, an ethyl group or a butyl group.

In the general formula (1), the group represented by X is a benzoyl group, a hydroxybenzoyl group,
Benzoyl group such as dihydroxybenzoyl group, hydroxymethoxybenzoyl group or hydroxymethoxysulfoxybenzoyl group or benzotriazolyl group, benzotriazolyl group such as hydroxybenzotriazolyl group or sulfoxybenzotriazolyl group Group.

In the general formula (2), in the 2-hydroxy-phenyl group represented by D, the substituent is a halogen atom such as a chlorine atom or a bromine atom, or an alkyl group such as a methyl group or an ethyl group; A sulfonamide group, a nitro group, an acylamino group such as an acetylamino group, or 4-amino-6
A triazinylamino group such as -hydroxy-triazinylamino group, a carboxylic acid group or a sulfonic acid group.

In the general formula (2), in the 2-carboxy-phenyl group represented by D, examples of the substituent include a chlorine atom, a nitro group, a carboxy group and a sulfoxy group.

In the general formula (2), the group represented by Q is a hydrogen atom or a phenyl group such as a phenyl, carboxyphenyl, sulfoxyphenyl, nitrocarboxyphenyl or nitrosulfoxyphenyl group. Is raised.

In the general formula (2), the group represented by E is chlorophenyl, nitrophenyl, chloronitrophenyl, carboxyphenyl, sulfoxyphenyl, nitrocarboxyphenyl, nitrosulfoxyphenyl. Group, dimethoxyaminophenyl group,
And phenyl groups such as methylethoxyaminophenyl group and diaminosulfoxyphenyl group.

In the general formula (2), the group represented by E is pyridine such as 2,6-dihydroxypyridine, 2,6-dianilinopyridine, 2,6-dihydroxy-4-methyl-5-cyanopyridine or Pyrazoles such as 1-sulfoxyphenyl-3-methyl-5-hydroxypyrazole.

In the general formula (2), the group represented by G is a hydrogen atom, a methyl group, an ethyl group,
An alkyl group such as a butyl group, or a biphenylamino group such as a nitrosulfoxyanilinophenyl group or a nitrocarboxyanilinophenyl group, or o, o
And an azophenyl group such as a '-dihydroxy-sulfoxy-phenylazophenyl group, a sulfoxyphenylazo-hydroxy-phenyl group, a pyrazolylazophenyl group, or a pyridinylazophenyl group.

In the general formula (3), the substituent in the 2-hydroxy-phenyl group represented by J is a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group or an ethyl group, or a sulfone. Amide group, nitro group, acylamino group such as acetylamino group, or 4-amino-6-
Examples thereof include a triazinylamino group such as a hydroxy-triazinylamino group, a carboxylic acid group, and a sulfonic acid group.

In the general formula (3), in the 2-carboxy-phenyl group represented by J, examples of the substituent include a chlorine atom, a nitro group, a carboxy group and a sulfoxy group.

In the general formula (3), the group represented by K includes a halogen atom such as a chlorine atom and a bromine atom;
Or an alkyl group such as a methyl group or an ethyl group, a sulfonamide group, a nitro group, or an acylamino group such as an acetylamino group;
A triazinylamino group such as -amino-6-hydroxy-triazinylamino group or a 2-hydroxy-phenyl group which may be substituted with a carboxylic acid group or a sulfonic acid group, or an alkyl group such as a methyl group or an ethyl group; Groups, or methoxy groups, alkoxy groups such as ethoxy groups, or acetylamino groups, acylamino groups such as benzoylamino groups, or triazinylamino groups such as 4-amino-6-hydroxy-triazinylamino groups, or Examples include a nitro group, a phenyl group substituted with a carboxylic acid group or a sulfonic acid group, and a 4,5-dicyano-2-imidazolyl group.

Examples of the group represented by Z in the general formula (3) include an imino group, a ureido group, a diiminochlorotriazinyl group, and a diiminohydroxytriazinyl group.

In the general formula (4), examples of the group represented by L include a hydrogen atom, a carboxyphenyl group, a sulfoxyphenyl group, a nitrocarboxyphenyl group, and a nitrosulfoxyphenyl group.

In the general formula (4), the group represented by M is a sulfoxyphenyl group, a methylsulfoxyphenyl group, an ethoxysulfoxyphenyl group, a dimethoxyaminophenyl group, a methylethoxyaminophenyl group, A phenyl group such as a diaminosulfoxyphenyl group or 2,6-dihydroxypyridine;
Pyridine such as 2,6-dihydroxy-4-methyl-5-cyanopyridine or 1
Pyrazoles such as -sulfoxyphenyl-3-methyl-5-hydroxypyrazole.

Although the dyes used in the present invention are shown in the form of the free acid in the above general formula, they are preferably in the form of a salt in actual use. Examples of the salt form include Li and N.
alkali metal salts or alkyl groups such as a and K;
Examples include salts of ammonium or salts of organic amines which may be substituted with a hydroxyalkyl group.

Specific examples of the dye used in the present invention are described below. The complexed metal is indicated in parentheses next to the dye number.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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For example, the dye represented by the above (1) -1 can be produced by the following steps. 2-Amino-6-chlorophenol-4-sulfonic acid was diazotized according to a conventional method (for example, New Dye Chemistry, Yutaka Hosoda, Gihodo Shuppan, pp. 412, lines 14 to 19), and 2,2-
'-Bishydroxy-4,4'-bismethoxy-6,6
After coupling with '-bissulfoxybenzophenone, the mixture was copper-containing using copper sulfate to obtain a dye represented by (1) -1. The dye represented by (2) -12 is
The J acid was diazotized in a conventional manner and coupled with 2,5-dimethoxyaniline at pH2. Then, after coupling with a separately diazotized 2-amino-6-nitro-4-sulfoxy-phenol at pH 10, the mixture was obtained using cobalt chloride to contain cobalt. The dye represented by (2) -17 is 2-amino-4,5-
The dicyano imidazole is diazotized according to a conventional method, coupled with sulfoxyphenyl gamma acid at a pH of 2 or less, and then separately diazotized 2-amino-4,5.
-It is obtained by coupling with dicyanoimidazole at pH 10 and then carrying out cobaltation as described above. The other dyes (1) and (2) and the dyes (3) and (4) can be obtained in the same manner.

The above general formula (1) in the recording liquid,
The content of the dye (2), (3) or (4) is preferably 0.2 to 8% by weight based on the total weight of the recording liquid.

As the aqueous medium used in the recording liquid of the present invention, water and a water-soluble organic solvent are used. Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, polyethylene glycol, glycerin, N-methylpyrrolidone, and diethylene glycol monosolvent. Butyl ether, isopropanol and the like.

These water-soluble organic solvents are usually used in the recording liquid in an amount of 1 to 50% by weight. On the other hand, water
Used 5 to 95%.

The recording liquid of the present invention contains 0.5 to 5% by weight.
By adding urea, 0.001 to 0.5% by weight of a surfactant and the like, quick drying after printing and printing quality can be further improved.

[0041]

The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention. In addition, a part shall represent the meaning of a weight part.

Example 1 15 parts of ethylene glycol
3 parts of isopropanol, the dye 3 of the formula (1) -1
Water was added to the mixture, and the pH was adjusted to 9 with an aqueous solution of lithium hydroxide to make the total weight 100 parts. The composition was sufficiently stirred and dissolved, filtered under pressure through a Teflon (registered trademark) filter having a diameter of 1 μm, and then deaerated by a vacuum pump and ultrasonic waves to prepare a recording liquid.

Using the obtained recording liquid, ink jet recording was carried out on electrophotographic paper using an ink jet printer (trade name: JetWind500C, product of Fuji Xerox Co., Ltd.) to obtain a magenta color print with a clear color tone. Further, the results of evaluation by the methods (a), (b), (c) and (d) are shown.

(A) Light fastness of recorded image: The recorded image was attached to the inside of the south window glass with the printed surface facing the glass surface for 2 weeks, but the discoloration of the recorded image was small.

(B) Weather resistance of recorded image: The recorded image was displayed for one month under a guard where the amount of traffic of the vehicle was large and it was not exposed to rain or direct sunlight, but the discoloration of the recorded image was small.

(C) Water resistance of recorded image: The recorded image was immersed in tap water for 5 minutes, but the bleeding of the recorded image was small.

(D) Storage stability of recording solution: The recording solution was sealed in a glass bottle and stored at room temperature for 3 months. As a result of visual observation, no coarse aggregate was found.

Example 2 Water was added to 5 parts of glycerin, 5 parts of diethylene glycol, 5 parts of N-methylpyrrolidone, and 5 parts of the dye of (2) -7, and the pH was adjusted with sodium hydroxide.
Was adjusted to 9 and the total amount was adjusted to 100 parts. The recording liquid was adjusted in the same manner as in Example 1. Example 1 using this recording liquid
As a result of printing in the same manner as described above, a black printed matter having a bluish color tone was obtained. For this printed matter, (a) and (b) of Example 1
(C) The evaluation according to (d) was performed. As a result, Example 1
In each case, good results were obtained.

Example 3 5 parts of ethylene glycol, 5 parts of polyethylene glycol (# 400), 1 part of diethylene glycol monobutyl ether, the dye (3) -1
Water was added to 5 parts, and the pH was adjusted to 10 with ammonia water to make the total amount 100 parts, and the recording liquid was prepared in the same manner as in Example 1. Printing was performed in the same manner as in Example 1 using this recording liquid, and as a result, a bluish-black printed matter was obtained. The printed matter was evaluated by (a) to (d) of Example 1.
As a result, similar to Example 1, good results were obtained.

Example 4 Water was added to 5 parts of glycerin, 5 parts of diethylene glycol, 5 parts of N-methylpyrrolidone and 5 parts of the dye of the above (4) -1, and the pH was adjusted with sodium hydroxide.
Was adjusted to 9 and the total amount was adjusted to 100 parts. The recording liquid was adjusted in the same manner as in Example 1. Example 1 using this recording liquid
As a result of printing in the same manner as in the above, a black printed matter having a brownish tone was obtained. For this printed matter, (a) and (b) of Example 1
(C) The evaluation according to (d) was performed. As a result, Example 1
In each case, good results were obtained.

Examples 5 to 52 In place of the dye (1) -1 used in Example 1, the above (1) 2 to (1)
-12, (2) -1 to (2) -6, (2) -8 to (2)
-31, (3) -2 to (3) -5, (4) -2 to (4)
The recording liquid was prepared and printed by the method of Example 1 except that the dye No.-4 was used, and the printed matter was evaluated. As a result, similar good results were obtained as in Example 1.

[0052]

The recording liquid of the present invention is used for ink-jet recording. Even when recording is performed on plain paper, a clear magenta-based, cyan-based or black-based printed matter can be obtained, and print density, light resistance, It has excellent weather (environmental gas) resistance and storage stability as a recording liquid.

Claims (5)

[Claims] (1) a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3) or a compound represented by the following general formula (4): A recording liquid containing at least one dye selected from metal complex dyes formed from the compounds shown and salts of Cu, Co, Ni or Fe. Embedded image [Wherein A and B each independently represent a 2-hydroxy-phenyl group which may have a substituent, a 2-carboxy-phenyl group which may have a substituent, or 4,5-dicyano- X represents a 2-imidazolyl group, X represents a benzoyl group or a benzotriazolyl group which may be substituted with a hydroxy group, an alkoxy group or a sulfonic acid group; P represents a hydrogen atom or an alkyl group; d represents 0 or 1, respectively. ] [In the formula, D represents a 2-hydroxy-phenyl group which may have a substituent, a 2-carboxy-phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group; Represents a phenyl group which may be substituted with a hydrogen atom or a carboxylic acid group, a sulfonic acid group or a nitro group, and E represents a substituted phenyl group, or a substituted pyridine group, or a substituted hydroxypyrazolyl group, or G represents a hydrogen atom or an alkyl group or a substituted phenyl group; Y represents a hydroxy group or an amino group; and e, f, g, and h each represent 0 or 1; Represents However, when the OH group is in the first position, NH-Q
When D is in the 7-position, D represents a substituted 2-hydroxy-phenyl group containing no nitro group, an optionally substituted 2-carboxy-phenyl group or a 4,5-dicyano-2-imidazolyl group. Represent. E + g represents 0 or 1. ] [In the formula, J represents a 2-hydroxy-phenyl group which may have a substituent, a 2-carboxy-phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group, K represents an optionally substituted phenyl group or a 4,5-dicyano-2-imidazolyl group, Z represents a linking group, and l and m represent 0 or 1. ] [Wherein, L represents a hydrogen atom or a phenyl group which may be substituted with a carboxylic acid group, a sulfonic acid group or a nitro group, and M represents an alkyl group, an alkoxy group, a halogen atom, a nitro group, a hydroxy group, Represents an amino group which may be substituted, a phenyl group which may be substituted with a carboxylic acid group or a sulfonic acid group, or a substituted pyridine group, or a substituted hydroxypyrazolyl group, and W represents a hydroxy group or an amino group. Represent
p, q, r, and t represent 0 or 1. ] 2. A compound represented by the following general formula (1):
A recording solution containing a metal complex dye formed from a salt of u, Co, Ni or Fe. Embedded image [Wherein A or B each independently represents a 2-hydroxy-phenyl group which may have a substituent, a 2-carboxy-phenyl group which may have a substituent or 4,
X represents a 5-dicyano-2-imidazolyl group, X represents a benzoyl group or a benzotriazolyl group which may be substituted with a hydroxy group, an alkoxy group or a sulfonic acid group; P represents a hydrogen atom or an alkyl group;
a, b and d each represent 0 or 1. ] 3. A compound represented by the following general formula (2):
A recording solution containing a metal complex dye formed from a salt of u, Co, Ni or Fe. Embedded image [In the formula, D represents a 2-hydroxy-phenyl group which may have a substituent, a 2-carboxy-phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group; Represents a phenyl group which may be substituted with a hydrogen atom or a carboxylic acid group, a sulfonic acid group or a nitro group, and E represents a substituted phenyl group, or a substituted pyridine group, or a substituted hydroxypyrazolyl group, or G represents a hydrogen atom or an alkyl group or an optionally substituted phenyl group, Y represents a hydroxy group or an amino group, and e, f, g, and h each represent a 4,5-dicyano-2-imidazolyl group. Represents 0 or 1. However, when the NH-Q group is at the 7-position when the OH group is at the 1-position, D is a substituted 2-hydroxy-phenyl group containing no nitro group, and an optionally substituted 2-carboxy-phenyl group. Group or 4,5
Represents a dicyano 2-imidazolyl group. E + g represents 0 or 1. ] 4. A compound represented by the following general formula (3):
A recording solution containing a metal complex dye formed from a salt of u, Ni, Co or Fe. Embedded image [In the formula, J represents a 2-hydroxy-phenyl group which may have a substituent, a 2-carboxy-phenyl group which may have a substituent or a 4,5-dicyano-2-imidazolyl group, K represents an optionally substituted phenyl group or a 4,5-dicyano-2-imidazolyl group, Z represents a linking group, and l and m represent 0 or 1. ] 5. A compound represented by the following general formula (4) and C
A recording solution containing a metal complex dye formed from a salt of u, Co, Ni or Fe. Embedded image [In the formula, L represents a hydrogen atom or a phenyl group optionally substituted with a carboxy group, a sulfoxy group or a nitro group, and M represents an alkyl group, an alkoxy group, a halogen atom, a nitro group, a hydroxy group, May represent an amino group, a phenyl group which may be substituted with a carboxylic acid group or a sulfonic acid group, or a substituted pyridine group, or a substituted hydroxypyrazolyl group; W represents a hydroxy group or an amino group;
p, q, r, and t represent 0 or 1. ]