JP2003292854A - Recording liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a recording liquid that gives mainly cyan color printings for the inkjet recording and that is excellent in hue, light fastness and weather resistance (environmental gas) as well as good in preservation stability. <P>SOLUTION: The recording liquid contains an aqueous medium and a dyestuff represented by formula (1) and/or (2) (wherein R1 and R2 each independently denotes a hydrogen atom and an alkyl group which may be substituted with a carboxylic acid group, X denotes an oxygen atom or an imino group, and R3 denotes an alkyl group, a phenyl group, a benzyl group, a phenetyl group or a naphtyl group, which may contain an alkoxy group or the like R4 denotes a hydrogen atom or an alkyl group which may be substituted with a carboxylic acid group or a sulfonic group, P denotes an alkyl group, an alkoxy group, a carboxylic acid group or a sulfonic group, n denotes 0 or 1 and M denotes a counterion). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a recording liquid. Specifically, it relates to a recording liquid suitable for inkjet.

[0002]

2. Description of the Related Art Ink jet recording methods have been widely used. A water-soluble dye or pigment is used as a colorant for the recording liquid used for this purpose. Pigments have excellent durability, but have a poor color tone, are inferior in abrasion resistance, and are anxious about dispersion stability or ejection stability. The water-soluble dye has a clear color tone, but has insufficient durability, particularly light resistance and weather resistance. In particular, for black and cyan colors, discoloration and fading, which is considered to be caused by an oxidizing gas in the air, is a serious problem. Therefore, various water-soluble dyes or durability improvers have been proposed. Regarding the water-soluble dye, for example, JP-A 2001-329,194
No. 2001-329,195, and for durability improving agents, JP-A Nos. 2002-60,667 and 2
Although many patents such as 002-2,098 have been proposed, they have not yet fully satisfied the market requirements. In particular, the cyan color is a very special hue compared to other colors, and it is extremely difficult to develop this hue.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a cyan color which is excellent in color tone and weather resistance and light resistance for ink jet recording, and a blue color, a black color using the cyan color,
It is intended to provide a recording liquid for green color.

[0004]

As a result of intensive studies, the present inventor has found that the use of a specific dye simultaneously satisfies the hue and durability of a cyan color, and has accomplished the present invention. That is, the gist of the present invention is the following general formula (1) and /
Alternatively, it exists in a recording liquid containing the compound represented by (2).

[Chemical 7] [In the formula, R1 and R2 each independently represent a hydrogen atom, a carboxylic acid group, a sulfonic acid group or an alkyl group which may be substituted with a quaternary ammonium group, X represents an oxygen atom or an imino group, and R3 represents an alkoxy group. Group, cyano group,
Alkoxycarbonyl group, carboxylic acid group, sulfonic acid group, or alkyl group which may have a quaternary ammonium group, phenyl group, benzyl group, phenethyl group or naphthyl group, which is represented by carboxylic acid group, sulfonic acid group or quaternary group. The ammonium group has a counterion. ]

[Chemical 8] [In the formula, R4 represents a hydrogen atom or an alkyl group which may be substituted with a carboxylic acid group or a sulfonic acid group;
Represents an alkyl group, an alkoxy group, a carboxylic acid group or a sulfonic acid group, n represents 0 or 1, and M represents a counter ion. ]

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The dye used in the present invention is selected from the dyes represented by the general formulas (1) and (2).

In the general formula (1), the group represented by R1 or R2 is a hydrogen atom or a carboxy group such as a methyl group, an ethyl group, a carboxymethyl group, a carboxyethyl group or a sulfoxymethyl group, Examples thereof include an alkyl group which may be substituted with a sulfoxy group or an alkyl group having a quaternary ammonium group such as hydroxypropyltrimethylammonium group.

In the general formula (1), the group represented by X is an oxygen atom or an imino group.

In the general formula (1), the group represented by R3 is an alkyl group such as a butyl group, a 2-ethylhexyl group or a dodecyl group, or an alkoxyalkyl group such as a methoxyethyl group or a propoxypropyl group. Or cyanoethyl group, or butyryloxyethyl group, acyloxyalkyl group such as benzoyloxyethyl group, or methoxycarbonylethyl group, alkoxycarbonylalkyl group such as hexyloxycarbonylpropyl group, or carboxymethyl group, carboxyethyl group, Succinic acid group, ε-caproic acid group, β-alanine group, alkyl group substituted with carboxy group or sulfoxy group such as sulfoxyethyl group, or quaternary ammonium group such as trimethylpropylammonium group A substituted alkyl group, or a benzoic acid group, a phthalic acid group, a sulfoxyphenyl group,
Aminobiphenyldisulfoxy group, nitrosulfoxyphenylaminophenyl group, nitrodisulfoxystilbenyl group, aminodisulfoxystilbenyl group,
A phenyl group substituted with a carboxy group or a sulfoxy group such as an aminosulfoxyphenoxyphenyl group, or a carboxy group or a sulfoxy group such as a sulfoxynaphthyl group, a disulfoxynaphthyl group or a dicarboxynaphthyl group And naphthyl group, sulfoxybenzyl group, sulfoxyphenethyl group, N-sulfoxyphenyl-N-methyl-aminopropyl group and the like.

In the general formula (2), the group represented by R4 is a hydrogen atom, an alkyl group such as a methyl group or a butyl group, or a carboxymethyl group, a carboxyethyl group or a sulfoxymethyl group. And an alkyl group which may be substituted with a carboxy group or a sulfoxy group.

In the general formula (2), the group represented by P is a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a carboxy group, Examples include sulfoxy group.

When the dye used in the present invention has a carboxy group or a sulfoxy group, it is preferably salt type in actual use, and examples of the salt type include alkali such as Li, Na and K. Examples thereof include metal salts, ammonium salts which may be substituted with an alkyl group and hydroxyalkyl group, and organic amine salts.

Specific examples of the dye used in the present invention are described below.

[Chemical 9]

[Chemical 10]

[Chemical 11]

The dyes of the general formula (1) used in the present invention are basically prepared by substituting 1,4-diamino-2,3-dichloroanthraquinone with cyano by a conventional method to give 1 , 4-Diamino-2,3-dicyano-anthraquinone was prepared, and cyano was hydrolyzed according to a conventional method to give 1,4-diamino-anthraquinone-2.
3-dicarbimide. It is then obtained by reacting with amines.

The dyes of the general formula (2) used in the present invention are basically, for example, according to the method described in Shin Dye Kagaku (Yutaka Hosoda, published by Gihodo Co., Ltd.), pages 220 to 222, for example: It is produced by reacting 1-amino-4-bromo-anthraquinone-2-sulfonic acid with sulfoxyanthranilic acid or aminophthalic acid, followed by ring closure.

The content of the dye of the general formula (1) or (2) in the recording liquid is 0.5 to 8% by weight based on the total weight of the recording liquid.

The dye represented by the general formula (3) or (4) used in the present invention is wet-pulverized as it is with a dispersant using, for example, a sand grinder utilizing glass beads, to obtain fine particles having a particle diameter of 1 micron or less. It can be used as a recording liquid by mixing it with a suitable water-soluble organic solvent.

Further, the dye represented by the general formula (3) or (4) used in the present invention is dissolved or dispersed in oil and then dispersed in water, or a mixture of the dye and wax is added as described above. Particles having a particle diameter of 1 μm or less can be formed into fine particles by the method described above, and an appropriate water-soluble organic solvent can be mixed and used as a recording liquid.

Oils used in combination with the dye represented by the general formula (3) or (4) to form fine particles include phosphoric acid ester, fatty acid ester, benzoic acid ester, phthalic acid ester and the like. Specific examples thereof include tributyl phosphate, methyl stearate, ethyl benzoate, dibutyl phthalate and the like. Examples of the method of dispersion include a method of dispersion using an emulsifier such as sucrose fatty acid ester, polyglycerin fatty acid ester and sorbitol fatty acid ester.

As the wax used in combination with the dye represented by the general formula (3) or (4) to form fine particles, those having a large polarity are preferable, and fatty acid amide,
Examples thereof include sucrose fatty acid ester, glycerin fatty acid ester, and sorbitol fatty acid ester. Specific examples thereof include stearic acid amide, glycerin distearic acid ester, and sucrose distearic acid ester.

The weight ratio of the dye to the oil or wax is 1:10 to 1: 100 by weight.

The dye represented by the general formula (5) or (6) used in the present invention is water-soluble and can be used as a recording liquid by mixing it with water and a water-soluble organic solvent as it is. it can.

On the other hand, by mixing the dye represented by the general formula (5) or (6) with a water-soluble resin or wax having an opposite charge, a poorly water-soluble or water-insoluble solid is obtained, and the solid is dispersed as a dispersant. At the same time, for example, it can be used as a recording liquid by wet pulverizing it with a sand grinder using glass beads to form fine particles having a particle diameter of 1 micron or less, and mixing an appropriate water-soluble organic solvent.

The water-soluble resin used for forming fine particles, which is used together with the dye represented by the general formula (5) or (6), has a cationic group and is polyallylamine. Polyvinylamine, polyethyleneimine,
Examples thereof include polyacrylic acid dimethylaminopropyl ester, polyacrylic acid trimethylammonium propylamide, polyhydroxypropyltrimethylammonium, and chitosan. On the other hand, examples having anionic groups include polystyrene sulfonic acid, styrene-maleic acid, polyacrylic acid, naphthalene sulfonic acid formalin condensate, and melamine sulfonic acid formalin condensate.

The wax used in combination with the dye represented by the general formula (5) or (6) for forming fine particles is dodecylamine as a wax having a cationic group. Stearylamine, dioctadecylamine, hydroxyethyldioctadecylamine, methyltrilaurylammonium chloride, trimethyloctadecylammonium chloride and the like can be mentioned. On the other hand, those having an anionic group include oleic acid, stearic acid, dodecyl sulfonic acid, nonylphenyl sulfonic acid, stearyl alcohol sulfonic acid ester, bisoctyl succinic acid ester sulfonic acid and the like.

The weight ratio of the dye to the resin or wax is 10: 1 to 1: 100 by weight.

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 mono. Examples include butyl ether and isopropanol.

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 is 4 in the recording liquid.
Used from 5 to 95%.

The recording liquid of the present invention contains 0.5 to 5% by weight.
Urea and 0.001 to 0.5% by weight of a surfactant and the like can further improve the quick-drying property after printing and the printing quality.

[0029]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. The parts mean the meanings of parts by weight.

Example 1 15 parts of ethylene glycol,
Water was added to 3 parts of isopropanol and 5 parts of the dye of the above (1) -1, and the pH was adjusted to 9 with an aqueous lithium hydroxide solution to make the total weight 100 parts. The composition was sufficiently stirred to dissolve it, filtered under pressure with a filter having a diameter of 1 μm, and then deaerated with a vacuum pump and ultrasonic waves to prepare a recording liquid.

Using the obtained recording liquid, an inkjet printer (trade name JetWind500C, product of Fuji Xerox Co., Ltd.) was used to perform inkjet recording on photo glossy paper for inkjet (product name, product of Fuji Xerox Co., Ltd.), and red A cyan print having a tone color tone was obtained. Further, the results of evaluation by the methods (a), (b), (c) and (d) are shown.

(A) Light resistance of recorded image: The recorded image was attached to the inside of the south window glass with the printing surface facing the glass surface for two weeks, but the discoloration and fading of the recorded image was small.

(B) Weather resistance of recorded image: The recorded image was posted for one month under a guard where there was a large amount of traffic and no 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 liquid: The recording liquid was sealed in a glass bottle and stored at room temperature for 3 months. As a result of visual observation, no coarse aggregate was observed.

[0036]

Example 2 Instead of the dye used in Example 1,
2.5 parts of the dye (1) -1 and CI Direct
As a result of evaluation in the same manner as in Example 1 except that 2.5 parts of Blue-86 was used, all were good results as in Example 1.

Comparative Example 1 Evaluation was made in the same manner as in Example 1 except that 5 parts of CI Direct Blue-86 was used instead of the dye used in Example 1, and as a result, the weather resistance was remarkably inferior.

Example 3 Water was added to 5 parts of glycerin, 5 parts of diethylene glycol, 5 parts of N-methylpyrrolidone, and 4 parts of the dye of the above (3) -1, and pH was adjusted with aqueous ammonia.
After adjusting to 9, the total amount was adjusted to 100 parts, and 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 reddish cyan printed matter was obtained. For this printed matter, (a) and (b) of Example 1
The evaluation according to (c) and (d) was performed. As a result, Example 1
Similar results were obtained in the same manner as in.

[Example 4] 5 parts of ethylene glycol, 5 parts of polyethylene glycol (# 400), the above (1)-
Add water to 4 parts of the dye of 2 and p.
After adjusting H to 9, the total amount was adjusted to 100 parts and the recording liquid was adjusted in the same manner as in Example 1. As a result of printing using this recording liquid in the same manner as in Example 1, a reddish cyan printed matter was obtained. For this printed matter, (a) and (b) of Example 1
The evaluation according to (c) and (d) was performed. As a result, Example 1
Similar results were obtained in the same manner as in.

Example 5 5 parts of ethylene glycol, 5 parts of polyethylene glycol (# 200), 5 of glycerin
Part, 2 parts of the dye of (1) -3 above, CI Food Bl
Water was added to 3 parts of ack-2, the pH was adjusted to 9 with an aqueous sodium hydroxide solution, and the total amount was adjusted to 100 parts.
A recording liquid was prepared in the same manner as in. As a result of printing using this recording liquid in the same manner as in Example 1, a bluish black printed material was obtained. For this printed matter, (a) and (b) of Example 1
The evaluation according to (c) and (d) was performed. As a result, Example 1
Similar results were obtained in the same manner as in.

[Comparative Example 2] As a result of evaluation in the same manner as in Example 4 except that 5 parts of CI Food Black-2 was used in place of the dye used in Example 5, the weather resistance was remarkably inferior.

Example 6 5 parts of ethylene glycol, 5 parts of glycerin, CI Pigment Blue-15: 1
Water was added to 3 parts and 1.5 parts of SMA1440H (styrene-maleic acid half ester copolymer, product of Arco Chemical Co., Ltd.) to make 98 parts, and then wet pulverized with a sand grinder for 72 hours using glass beads having a diameter of 1 mm. . A recording liquid was prepared by adding 2 parts of the dye (1) -4.
As a result of printing using this recording liquid in the same manner as in Example 1, a cyan printed matter was obtained. The printed matter was evaluated according to (a), (b), (c), and (d) of Example 1.
As a result, good results were obtained in the same manner as in Example 1.

[Example 7] 5 parts of ethylene glycol, 5 parts of glycerin, 3 parts of the dye of (2) -1 and SMA144
OH (styrene-maleic acid half ester copolymer,
Water was added to 1.5 parts of Arco Chemical Co., Ltd. to make 100 parts, and glass beads having a diameter of 1 mm were used to wet-mill for 72 hours with a sand grinder to prepare a recording liquid. As a result of printing using this recording liquid in the same manner as in Example 1, a reddish cyan printed matter was obtained. The printed matter was evaluated according to (a), (b), (c), and (d) of Example 1. As a result, good results were obtained in the same manner as in Example 1.

Example 8 (Preparation of colorant) 100 parts of stearic acid amide and (2)
After heat-mixing 10 parts of the dye of -2 at 100 ° C for 3 hours,
It was crushed to obtain 108 parts of a reddish cyan powder. (Preparation, printing, evaluation of recording liquid) Diethylene glycol 5
Part, glycerin 5 parts, the powder 10 parts, and sodium decyl sulfonate 5 parts by adding water to 100 parts, and then the diameter is 1 m.
The recording liquid was prepared by wet-milling for 72 hours with a sand grinder using m glass beads. As a result of printing using this recording liquid in the same manner as in Example 1, a reddish cyan printed matter was obtained. For this printed matter, (a) of Example 1
The evaluation according to (b), (c) and (d) was performed. As a result, good results were obtained in the same manner as in Example 1.

Example 9 (Preparation of colorant) 50 parts of chitosan was dissolved in 1000 parts of water. Dissolve 50 parts of the dye (1) -5 in 500 parts of water,
It was added to the chitosan aqueous solution. The blue precipitate was filtered, dried and pulverized to obtain 101 parts of a blue powder. (Preparation, printing, evaluation of recording liquid) Diethylene glycol 5
Parts, 5 parts of polyethylene glycol, 8 parts of the powder, and 5 parts of sodium naphthalene sulphonate formalin condensate were added to make 100 parts, and then wet pulverized with a sand grinder for 72 hours using glass beads having a diameter of 1 mm to record. The liquid was adjusted. As a result of printing using this recording liquid in the same manner as in Example 1, a reddish cyan printed matter was obtained. The printed matter was evaluated according to (a), (b), (c), and (d) of Example 1. As a result, good results were obtained in the same manner as in Example 1.

[Example 10] (Preparation of colorant) 50 parts of methyltrilauryl ammonium chloride was dissolved in 1000 parts of water. 50 parts of the dye of (1) -6 was dissolved in 500 parts of water and added to the above methyltrilauryl ammonium chloride aqueous solution. The blue precipitate was filtered, dried and pulverized to obtain 97 parts of a blue powder. (Preparation, printing, evaluation of recording liquid) Ethylene glycol 5
Water, 5 parts of N-methylpyrrolidone, 8 parts of the powder, 5 parts of condensate of sodium melamine sulphonate formalin to 100 parts, and then wet pulverized for 72 hours with a sand grinder using glass beads having a diameter of 1 mm. The recording liquid was adjusted by As a result of printing using this recording liquid in the same manner as in Example 1, a reddish cyan printed matter was obtained. The printed matter was evaluated according to (a), (b), (c), and (d) of Example 1. As a result, good results were obtained in the same manner as in Example 1.

[Example 11] (Preparation of colorant) 50 parts of styrene-sodium maleate was dissolved in 1000 parts of water. 50 parts of the dye of (1) -4 was dissolved in 500 parts of water and added to the styrene-sodium maleate aqueous solution. The blue precipitate was filtered, dried and pulverized to obtain 99 parts of a blue powder. (Preparation, printing, evaluation of recording liquid) Ethylene glycol 5
Water, 5 parts of glycerin, 6 parts of the powder, and 5 parts of sodium naphthalene sulfonate formalin condensate, and add water to obtain 100 parts.
After that, a glass bead having a diameter of 1 mm was used and wet pulverized with a sand grinder for 72 hours to prepare a recording liquid.
As a result of printing using this recording liquid in the same manner as in Example 1, a reddish cyan printed matter was obtained. For this printed matter,
The evaluation according to (a), (b), (c), and (d) of Example 1 was performed. As a result, good results were obtained in the same manner as in Example 1.

[0048]

INDUSTRIAL APPLICABILITY The recording liquid of the present invention is used for ink jet recording, and is excellent in light resistance and weather (environmental gas) resistance, and is also excellent in storage stability as a recording liquid.

Claims (10)

[Claims] 1. A recording liquid containing a dye represented by the following general formula (1) and / or (2). [Chemical 1] [In the formula, R1 and R2 each independently represent a hydrogen atom, a carboxylic acid group, a sulfonic acid group or an alkyl group which may be substituted with a quaternary ammonium group, X represents an oxygen atom or an imino group, and R3 represents an alkoxy group. Group, cyano group,
An acyloxy group, an alkoxycarbonyl group, a carboxylic acid group, a sulfonic acid group or an alkyl group which may have a quaternary ammonium group, a phenyl group, a benzyl group, a phenethyl group or a naphthyl group, a carboxylic acid group,
The sulfonic acid group or quaternary ammonium group has a counter ion. ] [Chemical 2] [In the formula, R4 represents a hydrogen atom or an alkyl group which may be substituted with a carboxylic acid group or a sulfonic acid group;
Represents an alkyl group, an alkoxy group, a carboxylic acid group or a sulfonic acid group, n represents 0 or 1, and M represents a counter ion. ] 2. A recording liquid containing a dye represented by the following general formula (3) and / or (4) or fine particles containing the dye. [Chemical 3] [In the formula, R5 and R6 each independently represent a hydrogen atom or an alkyl group, Y represents an oxygen atom or an imino group, R7 represents an alkoxy group, a cyano group, an alkyl group which may be substituted with an alkoxycarbonyl group, or phenyl. Represents a group, a benzyl group or a phenethyl group. ] [Chemical 4] [In the formula, R8 represents a hydrogen atom or an alkyl group, and Q
Represents a hydrogen atom, an alkyl group or an alkoxy group. ] 3. A recording liquid containing a dye represented by the following general formula (5) and / or (6) or fine particles containing the dye. [Chemical 5] [In the formula, R9 and R10 each independently represent a hydrogen atom, a carboxylic acid group, a sulfonic acid group or an alkyl group which may be substituted with a quaternary ammonium group, Z represents an oxygen atom or an imino group, and R11 represents a carboxylic acid group. It represents an alkyl group having an acid group, a sulfonic acid group or a quaternary ammonium group, a phenyl group, a benzyl group, a phenethyl group or a naphthyl group, and a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group has a counter ion. ] [Chemical 6] [In the formula, R12 represents a hydrogen atom or an alkyl group which may be substituted with a carboxylic acid group or a sulfonic acid group,
T represents a hydrogen atom, a carboxylic acid group or a sulfonic acid group, and M represents a counter ion. ] 4. The recording liquid according to claim 2, which contains fine particles containing a dye represented by the general formula (3) and / or (4) and a poorly water-soluble oil or wax. 5. The recording liquid according to claim 3, which contains fine particles containing the general formula (5) and / or (6) and a cationic group-containing polymer or wax, or an anionic group-containing polymer or wax. 6. The recording liquid according to claim 1, further comprising a metal phthalocyanine dye. 7. The recording liquid according to claim 1, further containing a polyazo black water-soluble dye containing a naphthol compound as a coupling component. 8. A copper phthalocyanine-based or nickel phthalocyanine-based dye is further contained.
The recording liquid according to 4 or 5. 9. A CI Direct Blue-86 and / or a CI Direct Blue-199 or a CI Acid Blue-9 or a CI Pigm.
ent Blue-15 is further contained,
Recording liquids described in 2, 3, 4 and 5. 10. The recording liquid according to any one of claims 1, 2, 3, 4, and 5, further containing CI Food Black-2 or CI DirectBlack-195.