JP3275671B2 - Ink jet recording liquid and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording liquid having excellent water resistance and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as an ink jet recording liquid, a solution in which a water-soluble dye such as an acid dye, a direct dye, or a basic dye is dissolved in a glycol solvent and water is often used. (JP-A-53-61412, JP-A-54-898)
11, JP-A-55-65269) As water-soluble dyes,
In order to obtain the stability of the recording liquid, those having high solubility in water are generally used. Therefore, the ink jet recorded matter generally has poor water resistance, and there is a serious problem that spilling of water easily causes dye bleeding of a recorded portion.

In order to improve such poor water resistance,
Attempts have been made to change the structure of the dye or to prepare a recording solution having a strong basicity. (Japanese Unexamined Patent Publication (Kokai) No. 56-57862) Further, it has been attempted to improve the water resistance by making good use of the reaction between the recording paper and the recording liquid. (Japanese Patent Laid-Open No. 50-490
04, JP-A-57-36692, JP-A-59-20669
6, JP-A-59-146889) These methods have a remarkable effect on certain types of recording paper, but since various recording papers are used in ink-jet recording, recording using a water-soluble dye is required. Liquids often do not provide sufficient water resistance of recorded matter.

[0004] Examples of recording liquids having good water resistance include those in which an oil-soluble dye is dispersed or dissolved in a high boiling point solvent and those in which an oil-soluble dye is dissolved in a volatile solvent. Environmentally disliked the emission of
Depending on the case where a large amount of recording is performed or where the apparatus is installed, the necessity of solvent recovery or the like may become a problem. Therefore, in order to improve the water resistance of the recorded matter, a recording liquid in which a pigment is dispersed in an aqueous medium has been developed. However, in the recording liquid for ink jet, the diameter of the discharge nozzle is becoming smaller as the resolution of the ink jet printer is increased, and it is used as a colorant in order to prevent clogging in the discharge nozzle. It is necessary to reduce the particle size of the pigment. In addition, recording liquids using pigments that have been developed so far often fail to produce recorded materials with clear hues, and in image formation on transparent substrates such as overhead projectors, clear hues comparable to dyes are required. There is a strong demand for a recording solution that can provide a colorant, and therefore, a pigment having a very fine particle diameter and a clear hue is required.

[0005] Ordinary inks are produced by dispersing with a solvent or resin using a dispersing machine such as a sand mill, a three-roll mill or a ball mill. The dispersion step is a step of loosening secondary particles, which are mainly aggregates of the primary particles of the pigment, to obtain a dispersion close to the state of the primary particles, and it is difficult to make the primary particles themselves into a finer pigment. . A high-speed sand mill is excellent in making the pigment finer, and depending on the pigment, it is possible to make the primary particles smaller, but in this case, a very large amount of energy is required.

As means for making primary particles fine,
A method of dissolving a pigment in a strong acid such as concentrated sulfuric acid or polyphosphoric acid and injecting it into cold water to precipitate fine pigment particles is known, but the finely divided pigment obtained by this method has a strong secondary Agglomeration is likely to occur, and a large amount of energy is often required in the dispersion step when producing an inkjet recording liquid. In addition, the strong secondary aggregation of the pigment often causes a problem in the ejection stability of the recording liquid.

Further, as a method of making the primary particles of the pigment fine, a mixture of the pigment and a water-soluble inorganic salt such as salt and sodium sulfate is moistened with a small amount of a solvent such as polyethylene glycol.
After grinding with a strong force such as a kneader, there is a method in which inorganic salts and a solvent are removed by washing with water and dried to obtain a pigment having fine primary particles. This method also requires a large amount of energy for grinding and a large amount of cost for treating a large amount of rinsing wastewater, which increases production costs.

[0008]

[Problems to be solved by the invention]

The present inventors have conducted intensive studies to solve the above problems, and as a result, by using the benzimidazolone-based yellow pigment obtained in the present invention as a coloring agent, it has a very clear hue and Thus, the present invention was found to be an inkjet recording liquid having excellent discharge stability in the present invention, and led to the present invention.

[0010]

[Means to solve the problem]

That is, the present invention relates to a recording liquid for ink-jet recording, in which a colorant is dispersed in an aqueous liquid, a diazotization reaction product of an aromatic amine represented by the following general formula (1): The present invention relates to an ink jet recording liquid characterized by using a benzimidazolone yellow pigment obtained by performing a coupling reaction with 5-acetoacetylaminobenzimidazolone represented by the following chemical formula (2).

[0012]

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(Where X and Y in the formula are each independently —H, —NO ₂ , —CONHR ¹ , —COOR ² ,
—CF ₃ , —CN, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 18 carbon atoms,
¹ is -H, an alkyl group or an aryl group having from 1 to 18 carbon atoms, R ² represents -H or an alkyl group having 1 to 6 carbon atoms. ) As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc., and as an alkyl group, a methyl group, an ethyl group, a butyl group, an isopropyl group, a hexyl group, etc.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, a stearyloxy group and an oleyloxy group.
R ¹ includes the above-mentioned alkyl group, phenyl group, tolyl group, ethylphenyl group and the like, and R ² includes the above-mentioned alkyl group and the like, but is not limited to these substituents.

[0014]

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[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The benzimidazolone-based pigment of the present invention has a very clear hue from bluish yellow to reddish yellow and can be widely used as a recording liquid for ink jet. The method for producing the benzimidazolone pigment of the present invention will be described in detail. Two or more aromatic amines as specifically shown in Table 1 (where the substitution position of the amino group is 1) are mixed at an arbitrary ratio. Preferably, different aromatic amines are mixed in a proportion of 1 mol% or more based on the total number of moles of the aromatic amine to be used, and the mixture is subjected to a diazotization reaction according to a conventional method, and then to 5-acetoacetylaminobenzimidazolone. It can be produced by a coupling reaction, and two or more kinds of compound molecules of the general formula (3) form pigment crystal particles.

The above-mentioned aromatic amine is usually subjected to a diazotization reaction in water in the presence of a mineral acid such as hydrochloric acid or sulfuric acid, preferably at a temperature of 20 ° C. or lower, to produce a diazo liquid. The diazotization reaction can also be carried out by using a hydrophilic solvent other than water, such as alcohol, acetone or dioxane, and similarly using sodium nitrite in the presence of a mineral acid such as hydrochloric acid or sulfuric acid. On the other hand, 5-acetoacetylaminobenzimidazolone is usually added to water together with an equimolar amount or more of sodium hydroxide or potassium hydroxide at room temperature to prepare a so-called coupler liquid as an aqueous solution. In addition, 5-acetoacetylaminobenzimidazolone is dissolved in water together with sodium hydroxide and potassium hydroxide, and an acid such as acetic acid is added to precipitate fine 5-acetoacetylaminobenzimidazolone from weak acidity. A neutral slurry liquid is often used as a coupler liquid. Further, similarly to the above diazotization reaction, a hydrophilic solvent such as alcohol, acetone and dioxane can be used. A coupling reaction (mixing coupling) is performed by injecting the diazo solution prepared by the above method at room temperature or under heating into the coupler solution, and the benzimidazolone pigment used in the inkjet recording solution of the present invention is produced. it can.

The coupling reaction proceeds smoothly under both acidic and alkaline conditions.
A clearer pigment can be obtained by adjusting the pH to pH 9 with hydrochloric acid or an aqueous sodium hydroxide solution. After the coupling reaction, the mixture is filtered and washed with water until neutral, and the resulting water cake is preferably used as a colorant without drying. Also, at the time of the coupling reaction, various surfactants such as nonionic, cationic, anionic and zwitterionic, various water-soluble resins such as rosin, various organic solvents such as butyl acetate, xylene and isobutyl alcohol are added, and the pigment is added. When the surface treatment is performed, aggregation can be prevented and dispersion can be facilitated. When performing surface treatment with rosin, after completing the coupling reaction, make the reaction solution alkaline, add various sodium rosin aqueous solutions, and further add calcium chloride or barium chloride etc. to form an insoluble rosin salt and coat the pigment surface . Instead of adding calcium chloride or barium chloride, the pigment surface may be acidified with a mineral acid or the like and the pigment surface may be coated with rosin. As the rosin, gum rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarated rosin, wood rosin and the like can be used.

[0018]

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[0019]

[Table 1]

A feature of the above-mentioned production method is that two or more aromatic amines are mixed at an arbitrary ratio and a diazotization reaction is carried out to perform a coupling reaction. The benzimidazolone pigment obtained by this method is , Different in chemical structure 2
It is a mixture of more than one kind of compound, but a simple mixture of each pure pigment obtained by individually diazotizing the mixed aromatic amine is the particle size, shape, surface area,
It has been found that physical properties such as crystallinity are completely different. This difference in properties is caused by the random arrangement of molecules with different chemical structures in the crystal structure.
In particular, as compared with a pure benzimidazolone pigment obtained by diazotizing one kind of aromatic amine without mixing and subjecting it to a coupling reaction, the primary particles of the pigment are extremely small, and therefore a pigment having an extremely large surface area can be obtained. Become.

As the ink-jet colorant, the finer the primary particles of the pigment used are, the more preferable it is. The benzimidazolone pigment of the present invention has been found to be most suitable as the ink-jet colorant. When the benzimidazolone pigment of the present invention is used in a recording liquid, the recording liquid does not clog the thin nozzles of an ink jet printer, discharge stability is extremely good, and the recorded matter has a clear hue and excellent It has excellent water and light resistance. In addition, since the benzimidazolone-based pigment of the present invention is uniform and fine pigment particles, when a film is formed using the coloring composition, the gloss value of the film surface becomes high. In addition, since it can be produced with extremely fine particles, there is no need to further reduce the size using a large amount of energy, which is industrially more advantageous. The benzimidazolone-based pigment obtained in the present invention can be easily dispersed without using a large amount of energy even in a dispersion step in producing a coloring composition using these pigments, in which aggregation of primary particles is extremely weak. The coloring composition can be manufactured at low cost.

The benzimidazolone pigment obtained by the above method is preferably used as a colorant without drying a water cake obtained by filtration. In some cases, it is preferable to use a water cake obtained by replacing water in the water cake with ion-exchanged water or distilled water as a coloring agent. By dispersing the water cake of the pigment with an ordinary disperser such as a sand mill, an ink jet recording liquid in which fine primary particles of the pigment are uniformly dispersed can be easily obtained.

In the present invention, a resin is used for favorably fixing the benzimidazolone pigment used as the colorant. As this resin, a water-soluble resin soluble in water or a water-dispersible resin dispersed in water is used alone or in combination. As such a resin, a water-soluble resin such as an acryl-based, styrene-acryl-based, polyester-based, polyamide-based, or polyurethane-based resin that is soluble in water and a resin that is dispersible in water are used. These resins are used in the recording liquid in an amount of 0.5 to 10% by weight, preferably 1 to 10% by weight.
Use 5% by weight. If the amount is less than this, sufficient fixing of the colorant cannot be performed. On the other hand, if the amount is larger than this amount, the ejection stability of the recording liquid may be reduced.

In the case of a water-soluble resin, the viscosity of the recording liquid tends to be high, but in the case of a water-dispersible resin, the viscosity can be suppressed to a low level. can get. If necessary, a neutralizing agent such as ammonium, an amine, or an inorganic alkali can be appropriately added to these resins and added. In the present invention, the aqueous solvent is one that prevents drying of the recording liquid at the nozzle portion, solidification of the recording liquid, and stable ejection of the recording liquid and drying of the nozzle over time. Examples of such aqueous solvents include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether. , 1,2-hexanediol, N-methyl {2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy}
4-methylpentanone and the like can be exemplified.

For the purpose of accelerating the drying of the recording liquid on paper, alcohols such as methanol, ethanol and isopropyl alcohol can be used. These aqueous solvents may be used alone or as a mixture to form 1 to 50% of the recording liquid.
Use within the range. As the water as a medium of the recording liquid, preferably, ion-exchanged water or distilled water from which metal ions and the like have been removed is used. When the printing medium of the recording liquid is paper, for example, a penetrant can be added in order to stop the penetration of the recording liquid into the paper and to increase the apparent dryness. Examples of such penetrants include glycol ethers such as diethylene glycol monobutyl ether described as aqueous solvents, alkylene glycols, polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, sodium dioctylsulfosuccinate, and the like. Can be used. These have sufficient effects when the used amount of the recording liquid is 5% or less.
If it is larger than this, bleeding of printing and paper missing (print through) occur, which is not preferable.

The antifungal agent is used to prevent the occurrence of fungi in the recording liquid, and includes sodium dehydroacetate, sodium benzoate, sodium pyridinethione {1} oxide, zinc pyridinethione {1} oxide, 1,2, ─Benzoisothiazoline─3─1,1─Benzoisothiazoline─
A 3-ion amine salt or the like is used. These use about 0.05 to 1.0% of the recording liquid. The chelating agent blocks metal ions in the recording liquid and prevents the deposition of metal at the nozzle portion and the insoluble matter in the recording liquid. The chelating agent is ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid. 0.005 to 0.5% of sodium salt of acid, diammonium salt of ethylenediaminetetraacetylic acid, tetraammonium salt of ethylenediaminetetraacetylic acid, etc.
Used.

Further, in order to adjust the pH of the recording liquid to a desired pH and obtain the stability of the recording liquid or the stability with the recording liquid piping in the recording apparatus, an adjusting agent such as an amine, an inorganic salt or ammonia, phosphorus A buffer such as an acid can be used. Also,
An antifoaming agent may be added to prevent the circulation or movement of the recording liquid and the generation of bubbles during the production of the recording liquid. In order to improve the dispersion of the pigment, the following surfactants may be added for use. As such a surfactant, an anionic, nonionic, cationic, or amphoteric surfactant can be used.

Examples of the anionic activator include fatty acid salts, alkyl sulfate salts, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, and alkyl phosphates. Salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester, etc. Can be illustrated.

Examples of the nonionic activator include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Examples thereof include glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine-based, and silicon-based nonionic activators. Examples of the cationic activator include an alkylamine salt, a quaternary ammonium salt, an alkylpyridinium salt, and an alkylimidazolium salt.

Examples of the amphoteric surfactant include alkyl betaine, alkyl amine oxide, phosphadyl choline and the like. As other additives, urea, dimethyl urea and the like can be added. Further, a dispersing aid such as a derivative of a pigment can be added. As pigment derivatives,
A basic compound in which a dialkylamino group or the like is introduced as a terminal substituent into an organic dye, for example, the following general formula (4):
(5) can be used, but the invention is not limited to these pigment derivatives.

[0031]

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(Where A is CO, SO ₂ , CH
A linking group such as ₂ NHCOCH ₂ , B represents an alkyl group, and n represents an integer. ) Dispersing aids such as pigment derivatives are excellent in dispersing pigments and have a great effect of preventing re-aggregation of pigments after dispersion, so that the characteristics of the benzimidazolone pigments of the present invention, which are extremely fine particles, are maximized. It is possible to produce an ink jet recording liquid having good temporal stability without drawing out or thickening with time. These derivatives may be added when dispersing the benzimidazolone pigment of the present invention. However, when producing the benzimidazolone pigment of the present invention, the aromatic amine of Table 1 and the following general The aromatic amines of the formulas (6) and (7) may be mixed, and the diazotization reaction and the coupling reaction may be simultaneously performed.

[0033]

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(Where A, B and n have the same meanings as in formulas (4) and (5)).

For the production of the recording liquid, a pigment water cake,
A dispersant, water or an aqueous resin, and an aqueous solvent are mixed and dispersed by a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, or the like. Alternatively, after kneading well with a two-roll mill in advance, the mixture is further dispersed in a sand mill or the like, diluted appropriately with water, and mixed with other additives to produce a recording liquid. Mixing and stirring can be performed by a high-speed disperser, emulsifier, or the like, in addition to stirring by a stirrer using ordinary blades. The mixed recording liquid is sufficiently filtered before or after dilution with a filter having a pore size of 1 μm or less. Preferably, it is filtered with a filter of 0.65 μ or less.

Prior to filtration of the filter, filtration by centrifugation can be used, which reduces clogging in filtration by the filter and facilitates filter replacement. The recording liquid is adjusted as a liquid having a viscosity of 0.8 to 15 cps (25 ° C.), depending on the type of the recording apparatus. The surface tension is 25 to 60 dyn / cm. PH
Is not particularly limited, but is in the range of 4 to 12, and 7 to 1
A weak alkalinity of 0 is preferred.

The recording liquid using the benzimidazolone-based pigment produced according to the present invention is water-based, but has extremely good water resistance, and is used for preparing documents in offices, marking on cardboard, numbering, recording bar codes, and the like. Can be used. The benzimidazolone pigments obtained in the present invention are C.I. I. Pigment Yellow 1
It has extremely excellent light resistance, heat resistance, and water resistance as compared with azo yellow pigments such as 2, 13, 14, 83, etc., and is extremely excellent as a colorant for an inkjet recording liquid for outdoor outboard. I have.

[0038]

The present invention will be specifically described below with reference to examples. In the examples, "parts" all indicate parts by weight, and "%"
All indicate% by weight.

Example 1 6.2 parts of 1-amino-2-methoxybenzene (aromatic amine 25 in Table 1), 1-amino-4-nitrobenzene (aromatic amine 3 in Table 1)
9 parts and 31 parts of 35% hydrochloric acid were added to 200 parts of ice water, then a solution prepared by dissolving 7.0 parts of sodium nitrite in 50 parts of water was added at 5 ° C. or lower, and the mixture was stirred for 1 hour to carry out a diazotization reaction to perform diazotization. Was prepared. Meanwhile, 23.3 parts of 5-acetoacetylaminobenzimidazolone and 16 parts of sodium hydroxide were dissolved in 1000 parts of ice water by stirring at 10 ° C. or less,
To this solution, 220 parts of a 12% acetic acid aqueous solution was added with stirring at 10 ° C. or lower to precipitate fine crystals of 5-acetoacetylaminobenzimidazolone, and a weakly acidic coupler liquid having a pH of about 5 was prepared. While stirring the coupler solution, the above diazo solution was added at 20 ° C. or lower and stirred for 3 hours, and further heated to 70 ° C. and stirred for 1 hour.
After filtration and washing, 123 parts (solid content: 30%) of the desired water cake of the benzimidazolone yellow pigment a was obtained.

Using the above-mentioned pigment water cake as a coloring agent, a concentrated recording liquid for ink jet was prepared according to the following formulation. Pigment a water cake (solid content 30% product) 47.0 parts Acrylic resin (Johncryl 62 solid content 34.6% manufactured by Johnson Polymer) 2.7 parts Surfactant (Kao Emulgen 420) 2.0 parts Ion Exchanged water 50.0 parts Glycerin 5.0 parts After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered through a 0.65 μm membrane filter to produce a recording liquid.

The above dispersion 13.3 parts Surfactant (Emulgen 420 manufactured by Kao) 0.2 parts Acrylic resin (Emapoly TYN-40 manufactured by Gifu Shellac 44.8% solid content) 3.0 parts Ethylene glycol 30.0 Part Sodium omazine (Ohlin) 0.15 part Sodium salt of ethylenediaminetetraacetylic acid 0.02 part Ion-exchanged water 63.5 parts This recording liquid (viscosity of recording liquid: 2.5 cps) is put into a cartridge of Epson 700VC2. As a result, clear recordings were obtained with good discharge stability without causing clogging of the discharge nozzles. Water was dropped on the recording surface to check the bleeding of the recording liquid.
There was no run-off, and it had sufficient water resistance.

The particle size distribution of the obtained recording liquid was measured with a laser diffraction type particle size distribution meter (“SALD-110” manufactured by Shimadzu Corporation).
0 "), the average particle size was 80 nm. Comparative Example 1 1-amino-4
129 parts of a pure benzimidazolone yellow pigment b water cake (solid content 28) was obtained in the same manner as in Example 1 above, using only 12.3 parts of 1-amino-2-methoxybenzene without mixing -nitrobenzene. %). Also, 1-
Using 13.8 parts of 1-amino-4-nitrobenzene without mixing amino-2-methoxybenzene, 123 parts of a pure benzimidazolone yellow pigment c water cake was prepared in the same manner as in Example 1 above. (Solid content 31%).
Instead of the water cake of the pigment a, a total of 48 parts (substantially the same composition as the water cake of the pigment a) obtained by mixing 25 parts of the water cake of the pigment b and 23 parts of the water cake of the pigment c were used. Similarly, a yellow recording liquid (viscosity of recording liquid: 3.1 cp)
s) was prepared, and recording was carried out using a 700 VC2 cartridge manufactured by Epson Corporation. As a result, remarkable clogging occurred in the discharge nozzle, and sufficient discharge stability could not be obtained.

The particle size distribution of the obtained recording liquid was measured by a laser diffraction type particle size distribution meter (“SALD-110” manufactured by Shimadzu Corporation).
0 "), the average particle size was 230 nm.

Example 2 1-Amino-2- of Example 1
1-amino-2 instead of 6.2 parts of methoxybenzene,
3. 5-dichlorobenzene (aromatic amine 15 in Table 1)
9 parts and 11.3 parts of 1-amino-4-trifluoromethylbenzene (aromatic amine 12 in Table 1) instead of 6.9 parts of 1-amino-4-nitrobenzene A coupling reaction was performed with 23.3 parts of 5-acetoacetylaminobenzimidazolone to obtain 160 parts (solid content: 25%) of a water cake of benzimidazolone yellow pigment d.

Instead of the water cake of the pigment a in Example 1,
Using 56 parts of a water cake of the pigment d, the treatment was carried out in the same manner as in Example 1, and the recording liquid for inkjet (viscosity of the recording liquid: 2.
7 cps). This recording liquid is supplied to an Epson 700V
When recording was performed in the cartridge C2, a clear recorded matter was obtained with good discharge stability without causing clogging of the discharge nozzle. Water was dripped on the recording surface to check the bleeding of the recording liquid. As a result, the bleeding of the recording liquid did not occur and the recording liquid had sufficient water resistance. As a result of measuring the particle size distribution of the obtained recording liquid with a laser diffraction type particle size distribution analyzer (“SALD-1100” manufactured by Shimadzu Corporation), the average particle size was 70 nm. (Comparative Example 2) In Example 2 above, 1-amino-2-
Without mixing trifluoromethylbenzene, using only 16.2 parts of 1-amino-2,5-dichlorobenzene,
In the same manner as in Example 1, 148 parts (27% solid content) of a pure benzimidazolone yellow pigment e water cake were obtained. Further, using only 16.1 parts of 1-amino-2-trifluoromethylbenzene without mixing 1-amino-2,5-dichlorobenzene, water of pure benzimidazolone yellow pigment f was similarly prepared. 160 parts (solid content 25%) of the cake were obtained. Instead of a water cake of pigment a, pigment e
A total of 55 parts of 16 parts of the water cake of Example 1 and 39 parts of the water cake of the pigment f were mixed (substantially the same composition as that of the pigment d), and Example 1 was used.
Yellow recording liquid (viscosity of recording liquid: 3.2 cps)
Was recorded in a 700 VC2 cartridge manufactured by Epson Corporation. When the recording was performed, remarkable clogging occurred in the discharge nozzle, and sufficient discharge stability could not be obtained.

The particle size distribution of the obtained recording liquid was measured with a laser diffraction type particle size distribution meter (“SALD-110” manufactured by Shimadzu Corporation).
0 "), the average particle size was 280 nm.

Example 3 1.4 parts of anthranilic acid (aromatic amine 9 in Table 1), 14.5 parts of 1-amino-2-trifluoromethylbenzene (aromatic amine 12 in Table 1) and 35% 31 parts of hydrochloric acid was added to 300 parts of ice water, then a solution of 7.0 parts of sodium nitrite dissolved in 50 parts of water was added at 5 ° C. or lower, and the mixture was stirred for 1 hour to perform a diazotization reaction to prepare a diazo liquid. On the other hand, 23.3 parts of 5-acetoacetylaminobenzimidazolone and 16 parts of sodium hydroxide are dissolved in 1500 parts of ice water by stirring at 10 ° C. or lower, and 220 parts of a 12% aqueous acetic acid solution is stirred at 10 ° C. or lower in this solution. The mixture was added all at once to precipitate fine crystals of 5-acetoacetylaminobenzimidazolone, and a weakly acidic coupler liquid having a pH of about 5 was prepared. While stirring the coupler solution, the above diazo solution was added at 20 ° C. or less, stirred for 3 hours, further heated to 80 ° C., stirred for 1 hour, washed with filtered water, dried at 80 ° C., and dried at 80 ° C. 133 parts of a water cake of imidazolone yellow pigment g (solid content 3
0%).

The following materials were placed in a sand mill and dispersed to prepare a concentrated recording liquid for ink jet. Pigment g water cake (solid content 30%) 50 parts Acrylic resin (Nippon Polymer F-157) 1.3 parts Dispersant (Zeneca Solsperse 27000) 0.5 parts Ion exchange water 74 parts Glycerin 5.8 parts Dimethyl After dispersing 0.1 part of ethanolamine, it was mixed with the following. After mixing, the mixture was filtered through a 3μ membrane filter, and then filtered through a 1μ membrane filter to produce a recording solution.

The above dispersion 25 parts Glycerin 20 parts Fungicide (Sodium Omazine, manufactured by Aurin Chemical Co.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Ethylene glycol monobutyl ether 0.5 parts Silicone emulsion type water-based defoaming agent 0.8 parts (Kao's “Anti-Home B20”) When this recording liquid (viscosity of the recording liquid: 2.5 cps) was placed in an Epson HG5130 cartridge and recording was performed, the discharge nozzles were clogged. Clear recordings were obtained with good ejection stability without any problems. Water was dropped on the recording surface to check the bleeding of the recording liquid.
There was no run-off, and it had sufficient water resistance.

The particle size distribution of the obtained recording liquid was measured using a laser diffraction type particle size distribution meter (“SALD-110” manufactured by Shimadzu Corporation).
0 "), the average particle size was 80 nm. (Comparative Example 3) 1-amino-2 was prepared by the above-mentioned method for synthesizing pigment g.
127 parts of a pure benzimidazolone yellow pigment h water cake (solid content 30%) was prepared in the same manner as in Example 3 above, using only 13.7 parts of anthranilic acid without mixing trifluoromethylbenzene. Obtained. Instead of the water cake of the pigment g, a total of 59.1 parts (substantially the same composition as the pigment g) obtained by mixing 4.8 parts of the water cake of the pigment h and 54.3 parts of the water cake of the pigment f of Comparative Example 2 was used. A yellow recording liquid (viscosity of the recording liquid: 3.4 cps) was prepared in the same manner as in Example 3, and the liquid was recorded in a cartridge of HG5130 manufactured by Epson Corporation. Sufficient ejection stability could not be obtained.

The particle size distribution of the obtained recording liquid was measured by a laser diffraction type particle size distribution meter (“SALD-110” manufactured by Shimadzu Corporation).
0 "), the average particle size was 310 nm.

Example 4 In place of 1.4 parts of anthranilic acid in Example 3, 1-amino-benzene-3,5-
10. Ethyl dicarboxylate (aromatic amine 11 in Table 1)
8 parts, 1-amino-2-trifluoromethylbenzene 1
Similarly, using 6.4 parts of 1-amino-4-chlorobenzene (aromatic amine 14 in Table 1) instead of 4.5 parts, 23.3 parts of diazotization reaction and 5-acetoacetylaminobenzimidazolone were performed. With a water cake 12 of benzimidazolone yellow pigment i
8 parts (solid content 32%) were obtained.

The following materials were placed and dispersed in a paint shaker to prepare a concentrated recording solution for inkjet. Pigment i water cake (solid content 32%) 47 parts Acrylic resin (Johncryl 62 manufactured by Johnson Polymer 62 solid content 31%) 3.0 parts Dispersant (Kao Emulgen A-90) 1.0 part Ion exchange water 50 parts Glycerin 6.0 parts After dispersion, they were mixed with the following. After mixing, the mixture was filtered through a 3μ membrane filter, and then filtered through a 1μ membrane filter to produce a recording solution.

The above dispersion 13.5 parts Dispersant (Emulgen A-90 manufactured by Kao) 0.2 part Acrylic resin (W-215 manufactured by Nippon Polymer) 1.0 part Ethylene glycol 10.0 parts Fungicide (Olin Chemical) 0.15 parts of sodium salt of ethylenediaminetetraacetylic acid 0.02 parts 63.5 parts of ion-exchanged water This recording liquid (viscosity of recording liquid: 1.6 cps) is put into a cartridge of Epson 700VC2 to record. As a result, clear recordings were obtained with good ejection stability without causing ejection nozzle clogging. Water was dropped on the recording surface to check the bleeding of the recording liquid.
There was no run-off, and it had sufficient water resistance.

When this ink was put into a cartridge of "thinkjet" manufactured by Hewlett-Packard Co., and recording was performed, a clear recorded matter with good discharge stability without causing clogging of the discharge nozzle was obtained. . Water was dripped on the recording surface to check the bleeding of the recording liquid. As a result, the bleeding of the recording liquid did not occur and the recording liquid had sufficient water resistance. Furthermore,
When the solid printing was performed on the OHP sheet, a clear and excellent transparent image was obtained. The particle size distribution of the obtained recording liquid was measured using a laser diffraction particle size distribution meter (“SA” manufactured by Shimadzu Corporation).
LD-1100 ”), the average particle size was 65 n.
m. (Comparative Example 4) In Example 3 above, 1-amino-benzene-3,5-dicarboxylate was mixed without adding 1-amino-benzene-3,5-dicarboxylic acid ethyl.
Using only 12.8 parts of amino-4-chlorobenzene,
In the same manner as in Example 3, 123 parts of a pure benzimidazolone yellow pigment j water cake (solid content: 30%) were obtained.
Also, without mixing 1-amino-4-chlorobenzene,
Using only 13.7 parts of 1-amino-benzene-3,5-dicarboxylic acid ethyl ester, 155 parts (29% solids) of a pure benzimidazolone yellow pigment k water cake were obtained in the same manner. Instead of the water cake of the pigment i, a total of 51 parts (substantially the same composition as the pigment i) obtained by mixing 22.5 parts of the water cake of the pigment j and 28.5 parts of the water cake of the pigment k were used. Similarly, a yellow recording liquid (viscosity of the recording liquid:
4.2 cps), and recording was performed in a 700 VC2 cartridge manufactured by Epson Corporation. As a result, remarkable clogging occurred in the discharge nozzle, and sufficient discharge stability could not be obtained. Further, when solid printing was performed on the OHP sheet, only an extremely opaque and unclear image was obtained.

The particle size distribution of the obtained recording liquid was measured using a laser diffraction type particle size distribution meter (“SALD-110” manufactured by Shimadzu Corporation).
0 "), the average particle size was 320 nm.

(Example 5) 8.8 parts of anthranilic acid (aromatic amine 9 in Table 1), 4.8 parts of 1-amino-2-trifluoromethylbenzene (aromatic amine 12 in Table 1),
2.5 parts of 1-amino-2-methoxybenzene (aromatic amine 25 in Table 1) and 31 parts of 35% hydrochloric acid were added to 200 parts of ice water.
Then, a solution prepared by dissolving 7.0 parts of sodium nitrite in 50 parts of water was added at 5 ° C. or lower and stirred for 1 hour to carry out a diazotization reaction to prepare a diazo liquid. On the other hand, ice water 150
0 part is 5-acetoacetylaminobenzimidazolone 2
3.3 parts and 16 parts of sodium hydroxide are dissolved by stirring at 10 ° C. or less, and 220 parts of a 12% aqueous acetic acid solution is added to 1 part of the solution.
With stirring at 0 ° C. or less, fine crystals of 5-acetoacetylaminobenzimidazolone were added at a stretch to precipitate fine crystals,
A slightly acidic coupler solution of about pH 5 was prepared. While stirring this coupler liquid, the above diazo liquid was heated at 20 ° C.
After stirring for 3 hours, further heating to 80 ° C. and stirring for 1 hour, the mixture was filtered and washed with water, and 123 parts of a desired benzimidazolone yellow pigment 1 water cake (solid content 3%) was added.
0%).

The following materials were placed and dispersed in a sand mill to prepare a concentrated recording liquid for ink jet. Aqueous cake of pigment 1 (solid content 30%) 80 parts Acrylic resin (61J manufactured by Johnson Polymer) 7 parts Dispersant (Emulgen A-90 manufactured by Kao) 4.0 parts In formula (5), n is 2 and B is methyl Pigment derivative 1.2 parts Ion exchange water 56 parts Diethylene glycol monobutyl ether 3 parts N-methyl-2-pyrrolidone 3 parts 2,4,7,9-tetramethyl-5-decyne-4,7-diol 1 Part Ethylene glycol 1 part After dispersing in a sand mill for 1 hour, it was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording liquid (viscosity: 2.1 cps, average particle size: 80 n).
m).

The above dispersion 13.0 parts Dispersant (Solsperse 27000 manufactured by Zeneca) 0.2 parts Acrylic resin (Emapoly TYN-40 manufactured by Gifu Shellac 44.8% solid content) 3.0 parts Diethylaminoethanol 0.2 parts Diethylene glycol 22.5 parts Proxel GXL (manufactured by Zeneca) 0.15 parts Ethylenediaminetetraacetylic acid 0.02 parts Ion-exchanged water 63.53 parts 2,4,7,9 tetramethyl-5-decyne 4,7 0.1 parts of Geodell When this ink was put into a cartridge of HG5130 manufactured by Epson and recording was performed, a good recorded matter was obtained. I dripped water on the recording surface and examined the bleeding of the ink.
The ink had sufficient water resistance without bleeding or running out of ink.

(Comparative Example 5) Instead of the water cake of the pigment l, the water cake 1 of the benzimidazolone pigment b of the comparative example 1
6.4 parts, a water cake of the benzimidazolone pigment f of Comparative Example 2 (30.2 parts) and a water cake of the benzimidazolone pigment h of Comparative Example 3 (39.5 parts) were mixed to give a total of 86.1 parts ( A yellow recording liquid (viscosity of the recording liquid: 4.2 cps) was prepared in the same manner as in Example 5 using the same composition as the pigment 1, and the recording was performed by placing the recording liquid in a cartridge of HG5130 manufactured by Epson Corporation. Remarkable clogging occurred in the discharge nozzle, and sufficient discharge stability could not be obtained. Further, when solid printing was performed on the OHP sheet, only an extremely opaque and unclear image was obtained.

The particle size distribution of the obtained recording liquid was measured by a laser diffraction type particle size distribution meter (“SALD-110” manufactured by Shimadzu Corporation).
0 "), the average particle size was 350 nm.

[0062]

By using a benzimidazolone pigment obtained by mixing two or more aromatic amines to carry out a diazotization reaction and then performing a coupling reaction with 5-acetoacetylaminobenzimidazolone. A recording material having good water resistance and a clear hue was obtained using water as a medium, and a recording liquid free from clogging of a discharge nozzle of an ink jet printer was obtained.
As a result, the restrictions on the recording medium are greatly reduced, and it has been expected that the use of the aqueous recording liquid, which has conventionally been often insufficient in water resistance due to the influence of the recording medium, can be expanded.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI C09B 67/22 B41J 3/04 101Y (56) References JP-A-9-48936 (JP, A) JP-A-9-40894 ( JP, A) Special Table Hei 6-509370 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00-11/20 C09B 29/32-29/33 C09B 41 / 00 C09B 67/22

Claims (6)

(57) [Claims] 1. An ink jet recording liquid in which a colorant is dispersed in an aqueous liquid, wherein the colorant is a diazotized product of two or more aromatic amines represented by the following general formula (1): And a benzimidazolone pigment obtained by a coupling reaction with 5-acetoacetylaminobenzimidazolone represented by the following chemical formula (2): Embedded image (Where X and Y in the formula are each independently —H, -N
_{^{O 2, -CONHR 1, -COOR 2}} , -CF 3, -C
N, represents a halogen atom, an alkyl group or an alkoxy group having 1 to 18 carbon atoms having 1 to 6 carbon atoms, R ¹ represents -H, an alkyl group or an aryl group having from 1 to 18 carbon atoms, R ²
Represents -H or an alkyl group having 1 to 6 carbon atoms. ) 2. The ink jet recording liquid according to claim 1, further comprising an aqueous resin. 3. The ink jet recording liquid according to claim 1, which is filtered by a filter having a pore size of 1 μm or less. 4. The ink jet recording liquid according to claim 1, wherein the colorant contains 0.1 to 10% by weight. 5. A liquid having a viscosity of 0.8 to 15 centipoise (25
C.). 6. The colorant and advance to prepare an aqueous dispersion of a concentrated form containing an aqueous resin, was diluted with water and additives, claim, characterized in that filtered with following filters pore size 1 [mu] m 1 6. The method for producing a recording liquid for an ink jet according to any one of claims 1 to 5 .