JPH09157569A - Ink jet recording liquid and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink jet recording liquid excellent in water resistance by using a benzimidazolone pigment obtained by coupling a diazotized aromatic amine with acetoacetylaminobenzimidazolone. SOLUTION: This recording liquid is prepared by coupling at least two diazotized aromatic amines represented by formula I (wherein X and Y are each H, NO2 , CN, a halogen, a 1-6C alkyl, a 1-8C alkoxyl or the like) with 5-acetoacetylaminobenzimidazolone to obtain a benzimidazolone pigment and dispersing this pigment in an aqueous medium. This ink can be stably delivererd from a nozzle and can give a clear hue. Since the pigment comprises mixed crystals of molecules of different chemical structures because at least two aromatic amines are used in the production of the pigment, its primary particles are very small in size and it is most suitable as a colorant for ink jet recording. Further, it is desirable that the particles are surface-treated with a surfactant, rosin or the like in the synthesis.

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 ink jet recording liquids, water-soluble dyes such as acid dyes, direct dyes and basic dyes dissolved in a glycol solvent and water are often used. (JP-A-53-61412, JP-A-54-898)
11, JP-A-55-65269) As a water-soluble dye,
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 big problem that the bleeding of the dye in the recorded portion easily occurs when water is spilled.

In order to improve such poor water resistance,
Attempts have been made to change the structure of the dye or to prepare a recording liquid with strong basicity. (JP-A-56-57862) It has also been attempted to improve the water resistance by making good use of the reaction between a recording paper and a recording liquid. (Japanese Patent Laid-Open No. 50-490
04, JP-A-57-36692, JP-A-59-2069.
6, JP-A-59-146889) These methods show remarkable effects on some kinds of recording papers, but various recording papers are used in recording by the ink jet method, and therefore recording using a water-soluble dye is used. In many cases, the liquid cannot obtain sufficient water resistance of the 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 inkjet, the diameter of the discharge nozzle is becoming smaller as the resolution of the inkjet printer is higher, and along with this, it is used as a colorant to prevent clogging of the discharge nozzle. It is necessary to reduce the particle size of the pigment. In addition, with the recording liquids that have been developed so far, it is often impossible to obtain a recorded matter with a clear hue, and when forming an image on a transparent substrate such as an overhead projector, a clear hue similar to that of a dye can be obtained. There is a strong demand for a recording liquid capable of obtaining the above-mentioned properties, and for that reason, a pigment having an extremely fine particle diameter and a clear hue is required.

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

Further, as a means for making primary particles finer,
A method is known in which a pigment is dissolved in a strong acid such as concentrated sulfuric acid or polyphosphoric acid and poured into cold water to precipitate fine particles of the pigment. Aggregation is likely to occur, and a large amount of energy is often required in the dispersion process when manufacturing the inkjet recording liquid. In addition, the ejection stability of the recording liquid often causes a problem due to the strongly secondary-aggregated pigment.

Further, as a method for making the primary particles of the pigment finer, a mixture of the pigment and a water-soluble inorganic salt such as salt or 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, the inorganic salt and solvent are washed off with water and dried to obtain a fine pigment having primary particles. This method also requires a large amount of energy for milling, and requires a large amount of cost to treat a large amount of washing wastewater, resulting in high production costs.

[0008]

[Problems to be solved by the invention]

As a result of intensive studies to solve the above problems, the inventors of the present invention have used the benzimidazolone yellow pigment obtained in the present invention as a coloring agent to give a nozzle having an extremely clear hue and a nozzle. The present invention has been completed by finding that the recording liquid for inkjet has excellent ejection stability.

[0010]

[Means for solving the problem]

That is, the present invention provides an ink jet recording liquid comprising a colorant dispersed in an aqueous liquid, wherein the colorant is a diazotized reaction product of an aromatic amine represented by the following general formula (1): The present invention relates to an inkjet recording liquid comprising a benzimidazolone-based yellow pigment obtained by a coupling reaction with 5-acetoacetylaminobenzimidazolone represented by the following chemical formula (2).

[0012]

Embedded image

(However, X and Y in the formula are independently of each other, --H, --NO ₂ , --CONHR ¹ , --COOR ² ,
-CF _3, represents -CN, 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 having 1 to 18 carbon atoms or an aryl group, and R ² represents -H or an alkyl group having 1 to 6 carbon atoms. ) As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and the like, and as the alkyl group, a methyl group, an ethyl group, a butyl group, an isopropyl group, a hexyl group and the like,
As the alkoxy group, a methoxy group, an ethoxy group, a butoxy group, a stearyloxy group, an oleyloxy group, and the like,
Examples of R ¹ include the above alkyl group, phenyl group, tolyl group, ethylphenyl group, and the like, and examples of R ² include the above alkyl group, but are not limited to these substituents.

[0014]

Embedded image

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The benzimidazolone pigment of the present invention has an extremely clear hue from bluish yellow to reddish yellow and can be widely used as an inkjet recording liquid. The method for producing the benzimidazolone-based pigment of the present invention will be described in detail. Two or more kinds of 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 with respect to the total number of moles of the aromatic amine used, and a diazotization reaction is carried out according to a conventional method, and then 5-acetoacetylaminobenzimidazolone is added. 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 with sodium nitrite in the presence of a mineral acid such as hydrochloric acid or sulfuric acid in water, preferably at 20 ° C. or lower to produce a diazo solution. The diazotization reaction can also be carried out by using a hydrophilic solvent other than water, such as alcohol, acetone or dioxane, and similarly by 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 solution 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. A neutral slurry liquid is often used as the coupler liquid. Further, a hydrophilic solvent such as alcohol, acetone or dioxane can be used as in the above diazotization reaction. A coupling reaction (mixed coupling) is carried out by injecting the diazo solution prepared by the above method into this coupler solution at room temperature or under heating to produce a benzimidazolone pigment used in the ink jet recording solution of the present invention. it can.

The coupling reaction proceeds smoothly under both acidic and alkaline conditions, preferably pH 3 to.
A clear pigment can be obtained by carrying out pH adjustment to pH 9 with hydrochloric acid or sodium hydroxide aqueous solution. After the coupling reaction, the mixture is filtered and washed to neutrality with water, and the resulting water cake is preferably used as a colorant without drying. In addition, during the coupling reaction, various surfactants such as nonionic, cation, anionic and amphoteric ions, various water-soluble resins such as rosin, various organic solvents such as butyl acetate, xylene and isobutyl alcohol are added to the pigment. When the surface treatment is performed, aggregation can be prevented and dispersion becomes easy. When the surface treatment is performed with rosin, after the coupling reaction is completed, the reaction solution is made alkaline and various rosin sodium aqueous solutions are added, and calcium chloride or barium chloride is further added to form an insoluble rosin salt to coat the pigment surface. . Instead of adding calcium chloride or barium chloride, the surface of the pigment may be acidified with a mineral acid or the like to coat the surface with rosin. As the rosin, gum rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin, wood rosin and the like can be used.

[0018]

Embedded image

[0019]

[Table 1]

The above-mentioned production method is characterized in that two or more kinds of aromatic amines are mixed at an arbitrary ratio to carry out a diazotization reaction to carry out a coupling reaction. The benzimidazolone pigment obtained by this method is , 2 with different chemical structures
Although it is a mixture of more than one kind of compound, a simple mixture of each pure pigment obtained by individually diazotizing a mixed aromatic amine is a particle size, shape, surface area,
It was found that the physical properties such as crystallinity are completely different. This difference in properties is brought about by the random arrangement of molecules having different chemical structures in the crystal structure.
In particular, compared with a pure benzimidazolone-based pigment obtained by subjecting one kind of aromatic amine to a diazotization reaction without mixing and then performing a coupling reaction, the primary particles of the pigment are remarkably small and therefore the surface area is remarkably large. Become.

As an ink jet colorant, the finer the primary particles of the pigment used are, the more preferable, and the benzimidazolone pigment of the present invention has been found to be most suitable as an ink jet colorant. When the benzimidazolone pigment of the present invention is used in the recording liquid, the recording liquid does not clog the thin nozzles of the inkjet printer, the ejection stability is extremely good, and the recorded matter is excellent in clear hue. It has water resistance and light resistance. Further, since the benzimidazolone 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. Further, since it can be manufactured with extremely fine particles, it is not necessary to further miniaturize it by using a large amount of energy, which is industrially more advantageous. The benzimidazolone-based pigment obtained in the present invention has extremely weak aggregation of primary particles and can be easily dispersed without using a large amount of energy even in a dispersion step when producing a coloring composition using these pigments. A colored composition can be manufactured at low cost.

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

A resin is used for favorably fixing the benzimidazolone pigment used as the colorant in the present invention. As this resin, a water-soluble resin that dissolves in water or a water-dispersible resin that is dispersed in water may be used alone or as a mixture. As such a resin, a water-soluble resin such as an acrylic resin, a styrene-acrylic resin, a polyester resin, a polyamide resin, or a polyurethane resin which is soluble in water and a resin which is dispersible in water are used. These resins are contained in the recording liquid in an amount of 0.5 to 10% by weight, preferably 1 to
5% by weight is used. If the amount is less than this amount, the colorant cannot be sufficiently fixed. If the amount is larger than this amount, the ejection stability of the recording liquid may be deteriorated.

A water-soluble resin tends to increase the viscosity of the recording liquid, but a water-dispersible resin can keep the viscosity low, and the water resistance of the recorded product is strong. 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 the recording liquid from drying at the nozzle portion and solidifies the recording liquid, and prevents stable ejection of the recording liquid and drying of the nozzle over time. Examples of such an aqueous solvent 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, ethylene glycol monoethyl ether. , 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-
4-methylpentanone etc. can be illustrated.

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 in a mixture of 1 to 50% of the recording liquid.
Use within the range. Water used as a medium of the recording liquid is preferably ion-exchanged water or distilled water from which metal ions are removed. When the material to be printed with the recording liquid is paper, a penetrant can be added to stop the permeation of the recording liquid into the paper and accelerate the apparent drying property. 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 used in an amount of 5% or less of the recording liquid,
If the amount is more than this range, the printing is bleeding and the paper is missing (print through), which is not preferable.

The mildew-proofing agent prevents the generation of mildew in the recording liquid, and includes sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zincpyridinethione-1-oxide, 1,2. --Benzisothiazoline-3-one, 1-Benzisothiazoline--
A 3-one amine salt or the like is used. These are used at 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 and the insoluble matter in the recording liquid. Ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid 0.005-0.5% of sodium salt of acid, diammonium salt of ethylenediaminetetraacetic acid, tetraammonium salt of ethylenediaminetetraacetic acid, etc.
Used.

In order to adjust the pH of the recording liquid to a desired pH and to stabilize the recording liquid or the stability with the recording liquid pipe in the recording apparatus, an adjusting agent such as amine, inorganic salt, ammonia, phosphorus, etc. A buffer solution 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 and used. As such a surfactant, an anionic, nonionic, cationic, or amphoteric surfactant can be used.

Examples of the anionic activator include fatty acid salt, alkyl sulfate ester salt, alkyl aryl sulfonate, alkyl naphthalene sulfonate, dialkyl sulfonate, dialkyl sulfosuccinate, alkyl diaryl ether disulfonate and alkyl phosphate. Salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester, etc. It can be illustrated.

As the nonionic activator, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl 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 zwitterionic activator include alkylbetaine, alkylamine oxide, phosphadylcholine and the like. Urea, dimethyl urea and the like can be added as other additives. Furthermore, a dispersion aid such as a pigment derivative can be added. As a pigment derivative,
A basic compound in which a dialkylamino group or the like is introduced into an organic dye as a terminal substituent, for example, the following general formula (4),
(5) and the like can be used, but the pigment derivatives are not limited to these.

[0031]

[Chemical 6]

(In the formula, A is CO, SO ₂ , CH
₂ NHCOCH ₂ or other linking group, B represents an alkyl group, and n represents an integer. ) Dispersion aids such as pigment derivatives are excellent in pigment dispersion and have a great effect of preventing reaggregation of the pigment after dispersion, so that the characteristics of the benzimidazolone pigment of the present invention having extremely fine particles can be maximized. It is possible to produce an inkjet recording liquid having good stability over time without causing withdrawal or thickening over time. Further, these derivatives may be added at the time of dispersing the benzimidazolone-based pigment of the present invention, but when the benzimidazolone-based pigment of the present invention is produced, the aromatic amine of Table 1 and the following general You may mix aromatic amines, such as Formula (6) and (7), and may perform a diazotization reaction and a coupling reaction at the same time.

[0033]

Embedded image

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

For the production of the recording liquid, pigment water cake,
A dispersant, water or an aqueous resin, and an aqueous solvent are mixed and dispersed with a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser or the like. Alternatively, after kneading well in advance with a two-roll mill, further dispersing with the above sand mill or the like, appropriately diluting with water, and mixing 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 with a filter having a pore size of 1 μm or less before or after dilution. Preferably, it filters with a filter of 0.65 micrometer or less.

Filtration by centrifugation may be used prior to filtration of the filter, which reduces clogging during 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 7-1
A weak alkalinity of 0 is preferred.

The recording liquid using the benzimidazolone pigment produced according to the present invention is remarkably excellent in water resistance even though it is water-based, and can be used for office document preparation, cardboard marking, numbering, bar code recording and the like. Can be used for. Further, the benzimidazolone pigments obtained in the present invention are C.I. I. Pigmen Yellow 1
It has extremely excellent light resistance, heat resistance, and water resistance as compared with azo yellow pigments such as 2, 13, 14, and 83, and is extremely excellent as a colorant for an inkjet recording liquid for outdoor outboards. There is.

[0038]

The present invention will be specifically described below with reference to examples. In the examples, all "parts" indicate parts by weight, and "%"
Indicates% 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) 6.
9 parts and 31 parts of 35% hydrochloric acid were added to 200 parts of ice water, and then a solution of 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 carry out a diazo solution. Was prepared. On the other hand, 23.3 parts of 5-acetoacetylaminobenzimidazolone and 16 parts of sodium hydroxide are dissolved in 1000 parts of ice water by stirring at 10 ° C. or lower,
220 parts of 12% acetic acid aqueous solution was added to this solution with stirring at 10 ° C. or lower to precipitate fine crystals of 5-acetoacetylaminobenzimidazolone to prepare a weakly acidic coupler solution having a pH of about 5. While stirring this coupler solution, the above diazo solution was added at 20 ° C. or lower and stirred for 3 hours, further heated to 70 ° C. and stirred for 1 hour,
After filtration and washing with water, 123 parts (solid content: 30%) of a desired water cake of the benzimidazolone type yellow pigment a was obtained.

Using the above pigment water cake as a colorant, a concentrated ink jet recording liquid was prepared according to the following formulation. Water cake of pigment a (solid content 30% product) 47.0 parts Acrylic resin (John Polymer 62 John Cryl 62 solid content 34.6%) 2.7 parts Surfactant (Kao's Emulgen 420) 2.0 parts Ion Exchanged water 50.0 parts Glycerin 5.0 parts After dispersion, they were mixed with the following. After mixing, the mixture was filtered through a 0.65μ membrane filter to prepare a recording liquid.

The above dispersion 13.3 parts Surfactant (Emulgen 420 manufactured by Kao) 0.2 parts Acrylic resin (Emapoly TYN-40 solid content 44.8% manufactured by Gifu Shellac) 3.0 parts Ethylene glycol 30.0 Part Sodium omazine (Ohlin) 0.15 part Ethylenediaminetetraacetic acid sodium salt 0.02 part Ion-exchanged water 63.5 parts This recording liquid (viscosity of recording liquid: 2.5 cps) was put into a cartridge of Epson 700VC2. When recording was performed by using a recording medium, a clear recorded matter was obtained with good ejection stability without causing clogging of the ejection nozzle. I drew water on the recording surface and checked for bleeding of the recording liquid.
It did not run off and had sufficient water resistance.

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).
The average particle size was 80 nm. (Comparative Example 1) 1-amino-4
129 parts of a pure benzimidazolone yellow pigment b water cake 129 parts (solids content 28%) in the same manner as in Example 1 above, using 12.3 parts of 1-amino-2-methoxybenzene without mixing nitrobenzene. %) Was obtained. Also, 1-
123 parts of a pure benzimidazolone-based yellow pigment c water cake (using 13.8 parts of 1-amino-4-nitrobenzene) without mixing with amino-2-methoxybenzene in the same manner as in Example 1 above. Solid content 31%) was obtained.
In place of the water cake of pigment a, a total of 48 parts (approximately the same composition as the water cake of pigment a) obtained by mixing 25 parts of the water cake of pigment b and 23 parts of the water cake of pigment c was used, and Similarly, a yellow recording liquid (viscosity of recording liquid: 3.1 cp)
When s) was prepared and recording was carried out with a 700VC2 cartridge manufactured by Epson Corporation, recording was carried out, significant discharge nozzle clogging occurred, 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).
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,
5-dichlorobenzene (aromatic amine 15 in Table 1) 4.
9 parts, 11.3 parts of 1-amino-2-trifluoromethylbenzene (aromatic amine 12 in Table 1) was used instead of 6.9 parts of 1-amino-4-nitrobenzene. A coupling reaction with 23.3 parts of 5-acetoacetylaminobenzimidazolone was carried out to obtain 160 parts of a water cake of benzimidazolone-based yellow pigment d (solid content 25%).

Instead of the water cake of pigment a of Example 1,
Using 56 parts of the water cake of pigment d and treating in the same manner as in Example 1, an ink jet recording liquid (viscosity of the recording liquid: 2.
7 cps) was obtained. This recording liquid is Epson 700V
When recording was carried out by placing it in a C2 cartridge, a clear recorded matter was obtained with good discharge stability without causing clogging of the discharge nozzle. When bleeding of the recording liquid was examined by dripping water on the recording surface, there was no bleeding of the recording liquid and no bleeding of the recording liquid, and sufficient water resistance was obtained. The average particle size was 70 nm as a result of measuring the particle size distribution of the obtained recording liquid with a laser diffraction type particle size distribution meter (“SALD-1100” manufactured by Shimadzu Corporation). (Comparative Example 2) In the above-mentioned Example 2, 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 (solid content: 27%) of a pure benzimidazolone type yellow pigment e water cake was obtained. Further, without mixing 1-amino-2,5-dichlorobenzene, only 16.1 parts of 1-amino-2-trifluoromethylbenzene was used in the same manner to prepare pure benzimidazone yellow pigment water f. 160 parts of cake (25% of solid content) were obtained. Instead of the water cake of pigment a, pigment e
A total of 55 parts of 16 parts of the water cake of No. 1 and 39 parts of the water cake of Pigment f (having almost the same composition as that of Pigment d) were mixed, and Example 1
Similar to the yellow recording liquid (viscosity of recording liquid: 3.2 cps)
Was prepared and put in a 700VC2 cartridge manufactured by Epson Corp., and recording was performed. As a result, remarkable clogging occurred at the ejection nozzle, and 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).
The average particle diameter was 280 nm.

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

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

Dispersion 25 parts Glycerin 20 parts Antifungal agent (Ohlin Chemical's Sodium Omazine) 0.15 parts Ethylenediaminetetraacetic acid sodium salt 0.02 parts Ethylene glycol monobutyl ether 0.5 parts Silicone emulsion type water-based antifoaming agent 0.8 part ("Anti-Home B20" manufactured by Kao) When this recording liquid (viscosity of the recording liquid: 2.5 cps) was put into a cartridge of HG5130 manufactured by Epson, recording was performed, and the ejection nozzle was clogged. A clear recorded matter was obtained with excellent ejection stability. I drew water on the recording surface and checked for bleeding of the recording liquid.
It did not run off and had sufficient water resistance.

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).
The average particle size was 80 nm. (Comparative Example 3) 1-amino-2
127 parts of a pure benzimidazolone yellow pigment h water cake (solids content 30%) in the same manner as in Example 3 above, but without mixing with trifluoromethylbenzene, using only 13.7 parts of anthranilic acid. Obtained. Instead of the water cake of pigment g, a total of 59.1 parts (approximately the same composition as pigment g) was obtained by mixing 4.8 parts of the water cake of pigment h with 54.3 parts of the water cake of pigment f of Comparative Example 2. A yellow recording liquid (viscosity of the recording liquid: 3.4 cps) was prepared in the same manner as in Example 3 and was put into a cartridge of HG5130 manufactured by Epson Corp., and recording was performed. However, 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).
The average particle size was 310 nm.

Example 4 In place of 1.4 parts of anthranilic acid of Example 3, 1-amino-benzene-3,5-
Ethyl dicarboxylate (aromatic amine 11 in Table 1) 11.
8 parts, 1-amino-2-trifluoromethylbenzene 1
Using 1-amino-4-chlorobenzene (aromatic amine 14 in Table 1) 6.4 parts instead of 4.5 parts, the same diazotization reaction and 5-acetoacetylaminobenzimidazolone 23.3 parts And a benzimidazolone type yellow pigment i water cake 12 is subjected to a coupling reaction with
8 parts (solid content 32%) were obtained.

The following raw materials were placed in a paint shaker and dispersed to prepare a concentrated recording liquid for inkjet. Water cake of pigment i (solid content 32%) 47 parts Acrylic resin (John Cryl 62 manufactured by Johnson Polymer, 31% solid content) 3.0 parts Dispersant (Emulgen A-90 manufactured by Kao) 1.0 part Ion-exchanged water 50 parts Glycerin 6.0 parts After dispersion, the following was mixed. After mixing, the mixture was filtered with a 3 μm membrane filter and then with a 1 μm membrane filter to prepare a recording liquid.

Dispersion 13.5 parts Dispersant (Emulgen A-90 manufactured by Kao) 0.2 parts Acrylic resin (W-215 manufactured by Nippon Polymer) 1.0 part Ethylene glycol 10.0 parts Antifungal agent (Aurin Chemical) Sodium omadine) 0.15 part Ethylenediaminetetraacetic acid sodium salt 0.02 part Ion-exchanged water 63.5 parts This recording liquid (viscosity of recording liquid: 1.6 cps) was put into a 700VC2 Epson cartridge for recording. As a result, a clear recorded material was obtained with good ejection stability without causing clogging of the ejection nozzle. I drew water on the recording surface and checked for bleeding of the recording liquid.
It did not run off and had sufficient water resistance.

Further, when this ink was put into a cartridge of "thinkjet" manufactured by Hewlett-Packard Co., and recording was carried out, a clear recorded matter was obtained with good ejection stability without causing clogging of the ejection nozzle. . When bleeding of the recording liquid was examined by dripping water on the recording surface, there was no bleeding of the recording liquid and no bleeding of the recording liquid, and sufficient water resistance was obtained. Furthermore,
When solid printing was performed on the OHP sheet, a transparent and clear image was obtained. The particle size distribution of the obtained recording liquid was measured by a laser diffraction type particle size distribution analyzer (“SA manufactured by Shimadzu Corporation”
LD-1100 "), the average particle size was 65n.
m. (Comparative Example 4) In the above-mentioned Example 3, 1-amino-benzene-3,5-dicarboxylate was not mixed, and 1-
Using only 12.8 parts amino-4-chlorobenzene,
In the same manner as in Example 3, 123 parts (solid content 30%) of a pure benzimidazolone type yellow pigment j water cake was obtained.
Also, without mixing 1-amino-4-chlorobenzene,
Using 23.7 parts of 1-amino-benzene-3,5-dicarboxylic acid ethyl ester alone, 155 parts (solid content 29%) of a pure benzimidazole yellow pigment k water cake was obtained in the same manner. A total of 51 parts (substantially the same composition as pigment i) obtained by mixing 22.5 parts of the water cake of pigment j and 28.5 parts of the water cake of pigment k was used in place of the water cake of pigment i, and Example 4 was used. Similarly, the yellow recording liquid (viscosity of the recording liquid:
4.2 cps) was prepared and recorded in an Epson 700VC2 cartridge, and recording was carried out. Sufficient clogging occurred at 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).
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.
A solution of 7.0 parts of sodium nitrite dissolved 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 solution. On the other hand, ice water 150
5-acetoacetylaminobenzimidazolone 2 in 0 parts
3.3 parts and 16 parts of sodium hydroxide were dissolved by stirring at 10 ° C. or below, and 220 parts of 12% acetic acid aqueous solution was added to 1 part of this solution.
While stirring at 0 ° C. or lower, added at once to precipitate fine crystals of 5-acetoacetylaminobenzimidazolone,
A weakly acidic coupler solution having a pH of about 5 was prepared. While stirring this coupler solution, add the above diazo solution to 20 ° C.
The mixture was added below and stirred for 3 hours, further heated to 80 ° C. and stirred for 1 hour, and then filtered and washed with 123 parts of a water cake of the desired benzimidazolone-based yellow pigment 1 (solid content: 3
0%).

The following raw materials were put into a sand mill and dispersed to prepare a concentrated recording liquid for inkjet. Water cake of pigment l (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 the general formula (5), n is 2 and B is methyl. Base pigment derivative 1.2 parts Ion-exchanged 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 Dispersed in a sand mill for 1 hour and then mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and then through a 0.45 μm membrane filter to prepare a recording liquid (viscosity 2.1 cps average particle size 80 n
m).

The above dispersion 13.0 parts Dispersant (Solspers 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 Ethylenediaminetetraacetic acid 0.02 parts Deionized water 63.53 parts 2,4,7,9-Tetramethyl-5-decyne-4,7- Diol 0.1 part When this ink was put in a cartridge of HG5130 manufactured by Epson Corporation and recording was carried out, a good recorded matter was obtained. I drew water on the recording surface and checked for ink bleeding.
There was no ink bleeding or running out, and it had sufficient water resistance.

(Comparative Example 5) Instead of the water cake of pigment l, the water cake 1 of benzimidazolone pigment b of Comparative Example 1
6.4 parts, 30.2 parts of a water cake of benzimidazolone pigment f of Comparative Example 2 and 39.5 parts of a water cake of benzimidazolone pigment h of Comparative Example 3 were mixed to give a total of 86.1 parts ( A yellow recording liquid (viscosity of recording liquid: 4.2 cps) was prepared in the same manner as in Example 5 using the same composition as Pigment 1), and recording was carried out by placing it in a cartridge of HG5130 manufactured by Epson Corporation. Sufficient clogging of the discharge nozzle occurred 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).
The average particle size was 350 nm.

[0062]

EFFECT OF THE INVENTION By using a benzimidazolone pigment obtained by mixing two or more kinds of aromatic amines to carry out a diazotization reaction, and then performing a coupling reaction with 5-acetoacetylaminobenzimidazolone, Using water as a medium, a recording liquid having good water resistance and giving a clear hue and having no clogging of the ejection nozzle of an inkjet printer can be obtained.
As a result, the restrictions on the recording medium are greatly reduced, and it can be expected that the applications of the aqueous recording liquid, which has been often insufficient in water resistance due to the influence of the recording medium, will be expanded.

Claims (6)

[Claims] 1. An ink jet recording liquid comprising a colorant dispersed in an aqueous liquid, wherein the colorant comprises two or more diazotized reaction products of an aromatic amine 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 (However, X and Y in the formula are independently -H, -N.
_{^{O 2, -CONHR 1, -COOR 2}} , -CF 3, -C
N, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, R ¹ represents —H, an alkyl group having 1 to 18 carbon atoms or an aryl group, and 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 with a filter having a pore diameter of 1 μm or less. 4. The ink jet recording liquid according to claim 1, which contains 0.1 to 10% by weight of a colorant. 5. A viscosity of 0.8 to 15 centipoise (25
C.) The ink jet recording liquid according to claim 1. 6. An ink jet recording characterized in that a concentrated aqueous dispersion containing a colorant and an aqueous resin is prepared in advance, diluted with water and additives, and filtered through a filter having a pore size of 1 μm or less. Liquid manufacturing method.