JPH09221616A - Recording liquid for ink-jet recording and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink-jet recording liquid having excellent dispesibility and ejection stability. SOLUTION: The objective ink-jet recording liquid is produced by dispersing a colorant in a water-based liquid. The colorant is a pigment produced by dissolving an organic pigment in sulfuric acid, pouring the solution into water and treating the precipitated fine powder in a 1-5C lower alcohol in the presence of a pigment-dispersing agent at 40-200 deg.C. The pigment-dispersing agent is at last one kind of compound expressed by the following formula I, formula II or formula III. Formula I: P-[X-(CH2 )n -N(R<1> )R<2> ]m , formula II: P-[X-(CH2 )n -Y]m , formula III: P-(SO3 H)m (P is an organic colorant residue or a heterocyclic group residue; X is SO2 NH or CONH; Y is SO3 H or COOH; R<1> and R<2> are each independently an alkyl or together form a heterocyclic group; (n) is an integer of 1-6; (m) is an integer of 1-3).

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 dispersibility, ejection stability and 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 are dissolved in a glycol solvent and water (JP-A-53-53).
61212, JP-A-54-89811, JP-A-55-6
5269), which is commonly used. As the water-soluble dye, a dye having high solubility in water is generally used in order to obtain the stability of the recording liquid. Therefore, the ink jet recorded matter generally has poor water resistance, and there is a 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 solution having a strong basicity (JP-A-56-57862). Further, it has 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. 50900/50).
4, JP-A-57-36692, JP-A-59-2069
6, JP-A-59-146889). Although these methods have a remarkable effect on a specific recording paper, they lack versatility in that they are restricted by the recording paper, and when a non-specific recording paper is used, a water-soluble dye is used. In many cases, the recording liquid used cannot obtain sufficient water resistance of the recorded matter.

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. There is a problem of the emission of sewage, which is not environmentally preferable.
In addition, there is a problem that solvent recovery or the like is required depending on a case where a large amount of recording is performed or where the apparatus is installed. 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 ink jet recording liquid, the nozzle diameter is becoming smaller as the printer is required to have high resolution, and accordingly, it is necessary to make the particle diameter of the colorant fine. Further, in image formation on a transparent base material such as an overhead projector, transparency as high as a dye is required, and therefore miniaturization is also required from the viewpoint of pigment color development.

In paints and inks, transparency is generally improved by decreasing the particle size of the pigment and increasing the degree of dispersion.
In a usual dispersing machine such as a sand mill, a three-roll mill, and a ball mill, when the primary particles are dispersed, the transparency cannot be further improved. This is because the dispersion process in a normal dispersing machine mainly breaks secondary particles into only primary particles,
To further improve the transparency, it is necessary to make the primary particles finer. In a high-speed sand mill, the primary particles can be made finer depending on the pigment used, but it is difficult to make the primary particles finer even if a very large amount of energy is applied.

As a means for making the primary particles finer, a method is known in which a pigment dissolved in a strong acid such as concentrated sulfuric acid or polyphosphoric acid is put into cold water to precipitate the pigment as fine particles. Since finely divided pigment causes strong secondary agglomeration when dried, it is very difficult to redisperse the dried pigment to primary particles, and as a method for improving dispersibility, heat treatment in a solvent such as alcohol is performed. It is known that this causes undesirable crystal growth, resulting in poor ejection stability.

[Problems to be Solved by the Invention]

The present invention solves the problems of the conventional methods described above, and relates to an ink jet recording liquid having good dispersibility and ejection stability, and a method for producing the same.

[Means for solving the problem]

That is, the present invention relates to an ink jet recording liquid in which a colorant is dispersed in an aqueous liquid, and as the colorant, a solution in which an organic pigment is dissolved in sulfuric acid is thrown into water to form fine precipitates. And a pigment dispersant, which is then treated in a lower alcohol having 1 to 5 carbon atoms at 40 to 200 ° C., is used for the ink jet recording liquid.

Furthermore, the present invention is the above ink jet recording liquid, wherein a solution of an organic pigment dissolved in sulfuric acid is thrown into continuously flowing water. Further, the present invention is the above-mentioned ink jet recording liquid, which contains an aqueous resin. Further, the present invention, the organic pigment, quinacridone pigment, phthalocyanine pigment, benzimidazolone pigment, diketopyrrolopyrrole pigment, perinone pigment, anthraquinone pigment, dioxazine pigment, perylene pigment, isoindolinone. The inkjet recording liquid is one kind selected from the group consisting of pigments.

Furthermore, the present invention is the above recording liquid for ink jet, wherein the pigment dispersant is at least one of the compounds represented by the following general formulas (1), (2) and (3). Formula (1) P- (X- (CH 2) n -N (R 1) R 2 ] _m Formula (2) P- [X- (CH _{2) n} -Y] _m Formula (3) P -(SO ₃ H) _m (wherein P is an organic dye residue or a heterocyclic residue, X is
Is SO ₂ NH or CONH, Y is SO ₃ H or C
OOH, R ¹ and R ² each independently form an optionally substituted alkyl group having 1 to 18 carbon atoms or R ¹ and R ² to form a heterocyclic ring which may have a substituent. Well,
n represents an integer of 1 to 6 and m represents an integer of 1 to 3. ]

Further, the present invention is the above ink jet recording liquid which is characterized by being filtered by a filter having a pore size of 1 μm or less. Further, the present invention is the above-mentioned water-dispersible inkjet recording liquid, characterized in that the solid content of the coloring agent is 0.1 to 10% by weight. Further, the present invention is the above-mentioned water-dispersed inkjet recording liquid, which has a viscosity of 0.8 to 15 mPa · s (25 ° C.).

Further, according to the present invention, a solution prepared by dissolving an organic pigment in sulfuric acid is poured into water to form a fine precipitate, which is then dispersed in a lower alcohol having a carbon number of 1 to 5 in the presence of a pigment dispersant.
A method for producing a water-dispersible inkjet recording liquid, which comprises diluting a concentrated aqueous dispersion containing a pigment and an aqueous resin treated at 200 ° C. with water and filtering the mixture with a filter having a pore size of 1 μm or less. Is.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, a solution in which an organic pigment is dissolved in sulfuric acid is poured into water to form a fine precipitate (hereinafter, this step is referred to as acid pasting), which is added to a lower alcohol in the presence of a pigment dispersant. The treated pigment treated at 40 to 200 ° C. is used as a colorant. Furthermore, by using a fine precipitate produced by throwing a solution of an organic pigment dissolved in sulfuric acid into continuously flowing water,
It has become possible to provide a recording liquid for inkjet which is more excellent in dispersibility and ejection stability than before.

When a liquid in which an organic pigment is dissolved in concentrated sulfuric acid is poured into water, a constant condition is always maintained from the first stage to the last stage of the operation by pouring into a continuously flowing water. As a result, not only fine particles are produced, but also those of constant quality can be obtained.

More specifically, the continuously flowing water used in the present invention means water flowing through a pipe or tube having a water pressure of 0.5 to 4.5 Kg / cm ² . The liquid in which the organic pigment is dissolved in concentrated sulfuric acid is added to this continuously flowing water quantitatively by using a water aspirator, or the liquid in which the organic pigment is dissolved in concentrated sulfuric acid is added to 0.5. It is preferable to pressurize to ˜4.5 Kg / cm ² and jet the water continuously flowing from the thin tube.

A solution prepared by dissolving an organic pigment in concentrated sulfuric acid is brought into contact with continuously flowing water to precipitate an organic pigment, and the aqueous solution is filtered to separate water from the product. Washed with an aqueous alkaline solution of, for example, caustic soda or caustic potassium to obtain a solid content of 10 to 10.
It is better to make a paste of 40% by weight.

Further, the above acid-pasted organic pigment is treated in a lower alcohol having 1 to 5 carbon atoms in the presence of 0.1 to 20% by weight of a pigment dispersant. An ink jet recording liquid in which a pigment treated by this method (hereinafter referred to as a treated pigment) is finely dispersed by dispersing with an ordinary disperser such as a sand mill as compared with the case where an untreated pigment is used. Can be easily obtained in a short time without spending a great deal of dispersion time. The pigment dispersant (B) prevents crystal growth of the pigment at the time of treatment at 40 to 200 ° C. in a lower alcohol having 1 to 5 carbon atoms, and dispersibility as fine crystals.
Improves ejection stability.

The organic dye constituting the organic dye residue represented by the general formulas (1) to (3) is a phthalocyanine-based organic dye,
Quinacridone series, Benzimidazolone series, Anthraquinone series, Dioxazine series, Diketopyrrolopyrrole series, Anthraquinone series, Ansanthron series, Indanthrone series,
There are flavansulone type, perinone type, perylene type, thioindigo type and the like. These dyes can be arbitrarily selected, but it is industrially advantageous to use those having a hue close to that of the pigment used. Examples of the heterocycle constituting the heterocyclic residue include thiophene, furan, xanthene, pyrrole, imidazole, isoindolinone, isoindoline, benzimidazolone, indole, quinoline, carbazole, acridine, acridone and anthraquinone. .

These organic dye residues or heterocyclic residues P
The substituent to be added to _{- (X- (CH 2) n} -N
(R ¹⁾ R ^2] _m or - [X- (CH _{2) n} -Y]
_m or —SO ₃ H _m , X is SO ₂ NH or CONH, Y is SO ₃ H or COOH, and R ¹ and R ² are each independently an optionally substituted alkyl group having 1 to 18 carbon atoms, Alternatively, R ¹ and R ² may form a heterocyclic ring which may have a substituent, n is an integer of 1 to 6, and m is
Represents an integer of 1 to 3.

The method for producing the pigment dispersant is as follows. First, a known method is applied to the organic dye or the heterocycle to --SO ₂ Cl--, --CO.
_{Cl -, - CH 2 Cl -} , - CH 2 NHCOCH 2 Cl
Introducing a substituent such as-, and-(CH in the general formula (1)
_{2) n} -N (R ¹⁾ is reacted with an amine component having a structure of R ² to obtain a pigment dispersing agent of the general formula (1). Examples of these amine components include N, N-dimethylaminomethyl, N, N-dimethylaminoethyl, N, N-dimethylaminopropyl, N, N-dimethylaminoamyl, N,
N-dimethylaminobutyl, N, N-diethylaminoethyl, N, N-diethylaminopropyl, N, N-diethylaminohexyl, N, N-diethylaminoethoxypropyl, N, N-diethylaminobutyl, N, N-diethylaminopentyl, N , N-dipropylaminobutyl, N, N-dibutylaminopropyl, N, N-dibutylaminoethyl, N, N-dibutylaminobutyl, N,
N-diisobutylaminopentyl, N, N-methyl-laurylaminopropyl, N, N-ethyl-hexylaminoethyl, N, N-distearylaminoethyl, N, N
-Amineylaminoethyl, N, N-distearylaminobutylamine or alcohol, or N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-amino Propyl-2-pipecoline, N
-Aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-aminomethylpiperidine, or N
-Hydroxymethylpiperidine, N-hydroxyethylpiperidine, N-hydroxypropylpiperidine, N-
Examples include hydroxyethylpipecoline, N-hydroxypropylpipecoline, N-hydroxymethylpyrrolidine, N-hydroxyethylmorpholine and N-hydroxybutylmorpholine. These pigment dispersants are preferably added in an amount of 0.1 to 20% by weight of the pigment when treated with a lower alcohol having 1 to 5 carbon atoms.

The solvent used in the present invention is a C1 to C5 lower alcohol, specifically methanol, ethanol, n-.
Propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol. These solvents are treated at 40 to 200 [deg.] C. while well stirring 1 to 30 times the solid content of the water paste having a solid content of 10 to 30 wt% of the pigment.

Further, when a finely divided pigment is treated with a lower alcohol having 1 to 5 carbon atoms, when a solvent which is not completely miscible with water is used, a nonionic surfactant,
For example, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, glycerin fatty acid ester, etc., and anionic surfactants such as fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl sulfosuccinate, etc. It is also possible to add 0.2 to 20% by weight to the pigment.

As a result, a fine organic pigment having good dispersibility can be obtained. In the present invention, an aqueous dispersion treated as described above is used as a colorant, and the colorant and an aqueous resin which is a binder resin are dispersed together by using an aqueous medium, or the colorant is previously prepared. Is dispersed with an aqueous resin that is a binder resin, and then diluted with an aqueous medium to produce an inkjet recording liquid.

The preferable particle size of the organic pigment is 1.0 μm or less when measured by laser scattering.
Further preferably, it is 0.2 μ or less. With such a particle size, the filtration operation in the production of the recording liquid is easy, and the sedimentation of the pigment in the recording liquid over time is reduced.

In the present invention, an aqueous resin is used for favorably fixing the colorant. As the aqueous resin, a water-soluble resin soluble in water or a water-dispersible resin dispersed in water is used alone or as a mixture. As such a water-based 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 aqueous resins are contained in the recording liquid in an amount of 0.5 to
It is preferably used in an amount of 10% by weight, more preferably 1 to 5% by weight. If the amount is less than 0.5% by weight, the colorant cannot be fixed sufficiently. Further, if it exceeds 10% by weight, the ejection stability of the recording liquid may be deteriorated. When a water-soluble resin is used as the water-based resin, the viscosity of the recording liquid tends to be increased, but with a water-dispersible resin, the viscosity can be suppressed to a low level, and the water resistance of the recorded material can be reduced. Can be improved. These resins are
If necessary, a neutralizing agent such as ammonia, amine and inorganic alkali can be appropriately adjusted and added.

In the present invention, the aqueous solvent used in addition to water prevents the recording liquid from drying at the nozzle portion and solidifying the recording liquid, and prevents stable jetting of the recording liquid and drying of the nozzle over time. It is a thing. As such an aqueous solvent, 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
Examples include —pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, and 4-methoxy-4-methylpentanone.

For the purpose of accelerating the drying of the recording liquid on paper, alcohols such as methanol, ethanol and isopropyl alcohol can also 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. As the medium of the recording liquid, deionized water or distilled water from which metal ions have been removed is used.

When the printing medium of the recording liquid is paper,
A penetrant can be added to stop the penetration of the recording liquid into the paper and to speed up the apparent dryness. Such penetrants include glycol ethers such as diethylene glycol monobutyl ether described as aqueous solvents, alkylene glycols, alkylene diols, polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, dioctylsulfosuccinic acid Sodium or the like can be used. These have sufficient effects when the used amount of the recording liquid is 5% or less, and when the amount is more than this, printing bleeding and paper loss (print through) occur, which is not preferable.

A fungicide may be added to the recording liquid of the present invention in order to prevent the generation of mold. Specifically, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazoline-3.
An amine salt of -1-one, 1-benzisothiazolin-3-one and the like are used. These are 0.05 to 1.
Use about 0%.

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 can 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 salts, alkyl sulfate salts, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, and polyphosphates. Oxyethylene 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 and the like can be exemplified.

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 alkyl betaine, alkyl amine oxide, phosphadyl choline and the like.

The dye can be used in such a form that there is no problem in water resistance and light resistance for the purpose of adjusting the hue of the pigment and imparting the concentration. Depending on the use of the dye, the dispersion stability of the pigment may be impaired, so it is necessary to limit the use to 40% or less, preferably 25% or less of the pigment.
Examples of the dye include water-insoluble dyes such as disperse dyes and oil-soluble dyes, direct dyes, acid dyes, basic dyes, and the like, which are insolubilized by lake formation, reactive dyes, metal-containing dyes, and the like.
These dyes are preferably purified dyes from which inorganic salts have been removed.

For the production of the recording liquid, a treated pigment dispersion, 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 thoroughly kneading with a two-roll mill, the mixture is further dispersed with the above sand mill or the like, appropriately diluted with water, and other additives are mixed 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 can be used before dilution or
After that, it is sufficiently filtered with a filter having a pore size of 3 μm or less. It is preferable to filter with a filter of 1.0 μm or less, more preferably 0.45 μm or less. Prior to filtration of the filter, it is also possible to remove those with a large particle size by centrifugation, which reduces clogging during filtration by the filter and prolongs the service life of the filter.

The recording liquid is preferably prepared as a liquid having a viscosity of 0.8 to 15 mPa · s (25 ° C.), though it depends on the type of recording device. Surface tension is 25-60 dyn /
cm is preferable, and PH is not particularly limited, but is 4 to 12
And weak alkalinity of 7 to 9 is preferable.

The recording liquid produced by the present invention is excellent in water resistance despite being water-based, and is excellent in dispersibility and ejection stability. Therefore, the recording liquid is suitably used as an inkjet recording liquid and is suitable for use in office documents. It can be used in the field of recorded materials such as making, symbols, cardboard marking, numbering, and bar codes.

[0040]

The present invention will be described below in further detail with reference to examples. In the examples, parts and% indicate parts by weight and% by weight, respectively. The types of pigment dispersants a to h used in the examples are shown in the table below. _{a: Q-SO 2 NH (} CH 2) 3 N (C 2 H 5) 2 b: Q-SO 2 NH (CH 2) 3 N (C 4 H 9) 2 c: Q-SO 3 H d: P _{-SO 2 NH (CH 2) 3} N (C 2 H 5) 2 e: P-SO 3 H f: B-CONH (CH 2) 3 N (C 2 H 5) 2 g: A-CONH (CH 2 ) ₃ N (C ₂ H ₅ ) ₂ However, Q is a quinacridone residue, P is a phthalocyanine residue, B is a benzimidazolone residue, and A is an anthraquinone residue.

Example 1 30 parts of Hosta Palm Pink E (quinacridone pigment Hoechst) and 98% sulfuric acid 3
Weigh 00 parts into a 1 liter glass beaker and stir for 1 hour to fully dissolve it. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate is filtered off, p
It was washed with water to H6.8 to obtain a water paste having a solid content of 10.50%. The obtained water paste, pigment dispersant a (0.9 parts) and isobutanol (300 parts) were placed in a flask equipped with a 1-liter cooling tube, and the mixture was stirred at room temperature for 30 minutes, then 90
Treated at ℃ for 1 hour. The pigment-treated product is collected by filtration, washed with water,
A pigment-treated product having a solid content of 30.0% was obtained. The obtained pigment-treated product and the following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid.

Red pigment (treated product of the above pigment, solid content 30.0%) 67.0 parts John Cryl 62 (styrene acrylic copolymer, solid content 34.0%, manufactured by Johnson Polymer Co., Ltd.) 13.1 parts Newcol 707 (nonionic) Surfactant Surfactant manufactured by Nippon Emulsifier Co., Ltd.) 2.0 parts Ion-exchanged water 17.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 2 30 parts of Hosta Palm Pink E (quinacridone pigment Hoechst) and 98% sulfuric acid 3
Weigh 00 parts into a 1 liter glass beaker and stir for 1 hour to fully dissolve it. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate is filtered off, p
It was washed with water to H6.8 to obtain a water paste having a solid content of 10.50%. The obtained water paste, pigment dispersant b (0.9 parts) and isobutanol (300 parts) were placed in a flask equipped with a 1-liter cooling tube and stirred at room temperature for 30 minutes, then 90
Treated at ℃ for 1 hour. The pigment-treated product is collected by filtration, washed with water,
A pigment-treated product having a solid content of 30.0% was obtained. Using the obtained pigment-treated product, the same operation as in Example 1 was carried out,
A water-dispersed inkjet recording liquid was prepared.

[Example 3] 30 parts of Hosta Palm Pink E (quinacridone pigment Hoechst) and 98% sulfuric acid 3
Weigh 00 parts into a 1 liter glass beaker and stir for 1 hour to fully dissolve it. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate is filtered off, p
It was washed with water to H6.8 to obtain a water paste having a solid content of 10.50%. The obtained water paste, pigment dispersant c (0.9 parts) and isobutanol (300 parts) were placed in a flask equipped with a 1-liter cooling tube and stirred at room temperature for 30 minutes, then 90
Treated at ℃ for 1 hour. The pigment-treated product is collected by filtration, washed with water,
A pigment-treated product having a solid content of 30.0% was obtained. Using the obtained pigment-treated product, the same operation as in Example 1 was carried out,
A water-dispersed inkjet recording liquid was prepared.

Comparative Example 1 The following raw materials were mixed and dispersed for 24 hours using a paint shaker to prepare a water-dispersed inkjet recording liquid concentrate. Hosta Palm Pink E (Quinacridone Pigment Hoechst) 20.0 parts Johncryl 62 (Styrene acrylic copolymer solids 34.0% Johnson Polymer Co., Ltd.) 13.1 parts Newcol 707 (Nonionic Surfactant Nippon Emulsifier Co., Ltd. 2.0 parts Ion-exchanged water 64.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 4 Lionol Blue FG-7
351 (Phthalocyanine pigment manufactured by Toyo Ink Mfg. Co., Ltd.) 3
0 parts and 300 parts of sulfuric acid are weighed into a 1-liter glass beaker and stirred for 1 hour to sufficiently dissolve them. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate is collected by filtration, washed with water to pH 7.0, and the solid content is 10.50%.
Of water paste was obtained. The obtained water paste, 0.9 parts of pigment dispersant and 300 parts of diethylene glycol were placed in a flask equipped with a 1-liter cooling tube, stirred for 30 minutes at room temperature, and then treated at 80 ° C. for 1 hour. The pigment-treated product was collected by filtration and washed with water to obtain a pigment-treated product having a solid content of 40.0%. The obtained pigment-treated product and the following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid.

Blue pigment (the above-mentioned pigment-treated product, solid content 40.0%) 50.0 parts John Cryl 61J (styrene acrylic copolymer, solid content 31.0% manufactured by Johnson Polymer Co., Ltd.) 16.4 parts Newcol B13 (nonionic) Surfactant surfactant (manufactured by Nippon Emulsifier Co., Ltd.) 5.0 parts Ion-exchanged water 28.6 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 5 Lionol Blue FG-7
351 (Phthalocyanine pigment manufactured by Toyo Ink Mfg. Co., Ltd.) 3
0 parts and 300 parts of sulfuric acid are weighed into a 1-liter glass beaker and stirred for 1 hour to sufficiently dissolve them. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate is collected by filtration, washed with water to pH 7.0, and the solid content is 10.50%.
Of water paste was obtained. The resulting water paste, 0.9 parts of pigment dispersant e, and 300 parts of diethylene glycol were placed in a flask equipped with a 1-liter cooling tube, stirred at room temperature for 30 minutes, and then treated at 80 ° C. for 1 hour. The pigment-treated product was collected by filtration and washed with water to obtain a pigment-treated product having a solid content of 40.0%. Using the obtained pigment-treated product, the same operation as in Example 4 was carried out to prepare a water-dispersed inkjet recording liquid.

Comparative Example 2 The following raw materials were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid. Lionol Blue FG-7351 (Phthalocyanine pigment manufactured by Toyo Ink Mfg. Co., Ltd.) 20.0 parts Johncryl 61J (styrene acrylic copolymer solid content 31.0% manufactured by Johnson Polymers Co., Ltd.) 16.4 parts Newcol B13 (nonionic interface) Activator (manufactured by Nippon Emulsifier Co., Ltd.) 5.0 parts Ion-exchanged water 58.6 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 6 Hosta Palm Yellow H3
30 parts of G (benzimidazolone pigment manufactured by Hoechst) and 300 parts of sulfuric acid are weighed into a 1-liter glass beaker and stirred for 1 hour to be sufficiently dissolved. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate was collected by filtration and washed with water to pH 7.0 to obtain a water paste having a solid content of 10.50%. The resulting water paste and pigment dispersant f
0.9 parts and 300 parts of isobutanol were placed in a flask equipped with a 1-liter cooling tube, stirred at room temperature for 30 minutes, and then treated at 90 ° C. for 1 hour. The pigment-treated product was collected by filtration and washed with water to obtain a pigment-treated product having a solid content of 35.0%. The obtained pigment-treated product and the following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid.

Yellow pigment (the above pigment-treated product, solid content 35.0%) 57.1 parts John Cryl 62 (styrene acrylic copolymer, solid content 31.0%, manufactured by Johnson Polymer Co., Ltd.) 8.8 parts PRYSURF A215-G (Anionic surfactant manufactured by Dai-ichi Kogyo Co., Ltd.) 7.0 parts Ion-exchanged water 27.1 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Comparative Example 3 The following raw materials were mixed and dispersed for 24 hours using a paint shaker to prepare a water-dispersed inkjet recording liquid concentrate. Hosta Palm Yellow H3G (Benz imidazolone pigment Hoechst Co.) 20.0 parts Johncryl 62 (styrene acrylic copolymer solid content 31.0% Johnson Polymer Co.) 8.8 parts Prysurf A215-G (anionic interface) Activator manufactured by Dai-ichi Kogyo Co., Ltd.) 7.0 parts Ion-exchanged water 64.2 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 7 Irgadine DPP RED
BO (diketopyrrolopyrrole pigment manufactured by Ciba Geigy)
0 parts and 300 parts of sulfuric acid are weighed into a 1-liter glass beaker and stirred for 1 hour to sufficiently dissolve them. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate is collected by filtration, washed with water to pH 7.0, and the solid content is 10.50%.
Of water paste was obtained. The obtained water paste, 0.9 parts of pigment dispersant a, and 300 parts of isobutanol were placed in a flask equipped with a 1-liter cooling tube, stirred at room temperature for 30 minutes, and then treated at 90 ° C. for 1 hour. The pigment-treated product is collected by filtration,
After washing with water, a pigment-treated product having a solid content of 30.0% was obtained. The obtained pigment-treated product and the following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid.

Red pigment (treated product of the above pigment, solid content 30.0%) 67.0 parts John Cryl 62 (styrene acrylic copolymer, solid content 34.0% Johnson Polymer Co., Ltd.) 13.1 parts Newcol 707 (nonionic) Surfactant Surfactant manufactured by Nippon Emulsifier Co., Ltd.) 2.0 parts Ion-exchanged water 17.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 8 Irgadine DPP RED
BO (diketopyrrolopyrrole pigment manufactured by Ciba Geigy)
30 parts of sulfuric acid and 300 parts of sulfuric acid are weighed into a 1 liter glass beaker and stirred for 1 hour to sufficiently dissolve them. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate was collected by filtration, washed with water to pH 7.0, and the solid content was 10.50.
% Water paste was obtained. The resulting water paste, 0.9 parts of pigment dispersant c, and 300 parts of isobutanol were placed in a flask equipped with a 1-liter cooling tube, stirred at room temperature for 30 minutes, and then treated at 90 ° C. for 1 hour. The pigment-treated product was collected by filtration and washed with water to obtain a pigment-treated product having a solid content of 30.0%. Using the obtained pigment-treated product, the same operation as in Example 7 was performed to prepare a water-dispersed inkjet recording liquid.

Comparative Example 4 The following raw materials were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid. Irgadine DPP RED BO (diketopyrrolopyrrole pigment manufactured by Ciba Geigy) 20.0 parts Johncryl 62 (styrene-acrylic copolymer solids 34.0% Johnson Polymer manufactured) 13.1 parts Newcol 707 (nonionic surfactant) Agent Nihon Emulsifier Co., Ltd.) 2.0 parts Ion-exchanged water 64.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 9 Hosta Palm Orange GR
30 parts (perinone pigment Hoechst) and 300 parts of sulfuric acid are weighed into a 1 liter glass beaker and stirred for 1 hour to sufficiently dissolve them. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate is filtered off and the pH
It was washed with water to 7.0 to obtain a water paste having a solid content of 10.50%. The obtained water paste, 0.9 parts of pigment dispersant b and 300 parts of isobutanol were placed in a flask equipped with a 1-liter cooling tube, stirred at room temperature for 30 minutes, and then at 90 ° C.
For 1 hour. The pigment-treated product was collected by filtration and washed with water to obtain a pigment-treated product having a solid content of 30.0%. The obtained pigment-treated product and the following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid.

Orange pigment (the above-mentioned pigment-treated product, solid content 30.0%) 67.0 parts John Cryl 62 (styrene acrylic copolymer solid content 34.0% Johnson Polymer Co., Ltd.) 13.1 parts Newcol 707 (nonionic) Surfactant Surfactant manufactured by Nippon Emulsifier Co., Ltd.) 2.0 parts Ion-exchanged water 17.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 10 Hosta Palm Orange G
30 parts of R (perinone pigment Hoechst) and 300 parts of sulfuric acid
Parts are weighed into a 1-liter glass beaker and stirred for 1 hour to sufficiently dissolve them. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate is filtered off and the pH
It was washed with water to 7.0 to obtain a water paste having a solid content of 10.50%. The obtained water paste, pigment dispersant c (0.9 parts) and isobutanol (300 parts) were placed in a flask equipped with a 1-liter cooling tube and stirred at room temperature for 30 minutes, and then at 90 ° C.
For 1 hour. The pigment-treated product was collected by filtration and washed with water to obtain a pigment-treated product having a solid content of 30.0%. Using the obtained pigment-treated product, the same operation as in Example 9 was carried out to prepare an inkjet recording liquid.

Comparative Example 5 The following raw materials were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid. Hosta Palm Orange GR (Perinone Pigment Hoechst Co., Ltd.) 20.0 parts John Kryl 62 (Styrene Acrylic Copolymer Solid Content 34.0% Johnson Polymer Co., Ltd.) 13.1 parts Newcol 707 (Nonionic Surfactant Japan Emulsifier 2.0 parts Ion-exchanged water 64.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 11 Chromophtal red A2B
(Anthraquinone pigment manufactured by Ciba Geigy) 30 parts and 9
300 parts of 8% sulfuric acid is weighed into a 1-liter glass beaker and stirred for 1 hour to sufficiently dissolve it. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate was collected by filtration and washed with water to pH 6.8 to obtain a water paste having a solid content of 10.50%. The obtained water paste and pigment dispersant g
0.9 parts and 300 parts of diethylene glycol were placed in a flask equipped with a 1-liter cooling tube, stirred at room temperature for 30 minutes, and then treated at 80 ° C. for 1 hour. The pigment-treated product was collected by filtration and washed with water to obtain a pigment-treated product having a solid content of 30.0%. The obtained pigment-treated product and the following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid. Red pigment (treated product of the above pigment, solid content 30.0%) 67.0 parts John Cryl 62 (styrene acrylic copolymer, solid content 34.0% Johnson Polymer Co., Ltd.) 13.1 parts Newcol 707 (nonionic surfactant) Agent Nihon Emulsifier Co., Ltd.) 2.0 parts Ion-exchanged water 17.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Comparative Example 6 The following raw materials were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid. Chromophthal red A2B (Anthraquinone pigment manufactured by Ciba Geigy) 20.0 parts John Cryl 62 (styrene acrylic copolymer solid content 34.0% manufactured by Johnson Polymer Co., Ltd.) 13.1 parts Newcol 707 (Nonionic surfactant Japanese emulsifier 2.0 parts Ion-exchanged water 64.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 12!
30 parts of Hosta Palm Violet RL Special (dioxazine pigment Hoechst) and 300 parts of sulfuric acid are weighed into a 1 liter glass beaker and stirred for 1 hour to sufficiently dissolve them. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate was collected by filtration, washed with water to pH 7.0 and the solid content was 1
A 0.50% water paste was obtained. The obtained water paste, 0.9 parts of pigment dispersant a, and 300 parts of isobutanol were placed in a flask equipped with a 1-liter cooling tube, stirred at room temperature for 30 minutes, and then treated at 90 ° C. for 1 hour. The pigment-treated product was collected by filtration and washed with water to obtain a pigment-treated product having a solid content of 35.0%. The obtained pigment treated product and the following raw materials are mixed and dispersed for 12 hours using a paint shaker,
A concentrated dispersion of the water-dispersed inkjet recording liquid was prepared.

Purple pigment (the above-mentioned pigment-treated product, solid content 35.0%) 57.1 parts JONCRYL 61J (styrene acrylic copolymer solid content 31.0%, manufactured by Johnson Polymer Co., Ltd.) 16.4 parts Emulgen A-90 ( Nonionic surfactant Kao Corporation) 5.0 parts Ion-exchanged water 21.5 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Example 13 Irgadine Red BPT
(Perylene pigment manufactured by Ciba Geigy) 30 parts and 300 parts of 98% sulfuric acid are weighed into a 1 liter glass beaker,
Stir for 1 hour to fully dissolve. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate was collected by filtration and washed with water to pH 6.8 to obtain a water paste having a solid content of 10.50%. The resulting water paste and pigment dispersant b0.
9 parts and 300 parts of diethylene glycol were put into a flask equipped with a 1-liter cooling tube, stirred at room temperature for 30 minutes, and then treated at 80 ° C. for 1 hour. The pigment-treated product is collected by filtration,
After washing with water, a pigment-treated product having a solid content of 30.0% was obtained. The obtained pigment-treated product and the following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid.

Red pigment (treated product of the above pigment, solid content 30.0%) 67.0 parts John Cryl 62 (styrene acrylic copolymer, solid content 34.0%, manufactured by Johnson Polymer Co., Ltd.) 13.1 parts Newcol 707 (nonionic) Surfactant Surfactant manufactured by Nippon Emulsifier Co., Ltd.) 2.0 parts Ion-exchanged water 17.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Comparative Example 8 The following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid. Irgadine Red BPT (Perylene pigment manufactured by Ciba Geigy) 20.0 parts John Cryl 62 (styrene acrylic copolymer solid content 34.0% manufactured by Johnson Polymer) 13.1 parts Newcol 707 (nonionic surfactant Japanese emulsifier (Manufactured by the company) 2.0 parts Ion-exchanged water 17.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

[Embodiment 14] Irgazi Yellow 2GLT
30 parts of E (isoindolinone pigment manufactured by Ciba-Geigy) and 300 parts of sulfuric acid are weighed into a 1 liter glass beaker and stirred for 1 hour to be sufficiently dissolved. The total amount of the dissolved solution was added dropwise over 1 minute through an aspirator connected to a water flow set at 3.50 Kg / cm ² with a gauge pressure. The precipitate was collected by filtration and washed with water to pH 7.0 to obtain a water paste having a solid content of 10.50%. The resulting water paste and pigment dispersant f
0.9 parts and 300 parts of diethylene glycol were placed in a flask equipped with a 1-liter cooling tube, stirred at room temperature for 30 minutes, and then treated at 80 ° C. for 1 hour. The pigment-treated product was collected by filtration and washed with water to obtain a pigment-treated product having a solid content of 40.0%. The obtained pigment-treated product and the following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid.

Yellow pigment (the above-mentioned pigment-treated product, solid content 40.0%) 50.0 parts Johncryl 61J (styrene acrylic copolymer, solid content 31.0% manufactured by Johnson Polymer Co., Ltd.) 16.4 parts Newcol B13 (nonionic) Surfactant surfactant (manufactured by Nippon Emulsifier Co., Ltd.) 5.0 parts Ion-exchanged water 28.6 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

Comparative Example 9 The following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous dispersion of an inkjet recording liquid. Irgazi Yellow 2GLTE (isoindolinone pigment manufactured by Ciba Geigy) 20.0 parts Johncryl 61J (styrene acrylic copolymer solid content 31.0% manufactured by Johnson Polymers) 16.4 parts Newcol B13 (nonionic surfactant) 5.0 parts ion-exchanged water 28.6 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is appropriately added to give a viscosity of 2.5 mP.
After being adjusted to as (25 ° C.) and surface tension of 40 dyn / cm, it was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. The above concentrated solution 12.5 parts Emmapoly-TYN-40 (styrene acrylic copolymer solid content 44.8%, manufactured by Gifu Shellac Manufacturing Co., Ltd.) 2.5 parts glycerin 20.0 parts ion-exchanged water 65.0 parts

The water-dispersible ink jet recording liquids of Examples 1 to 14 and Comparative Examples 1 to 9 were examined for average particle diameter as dispersibility, for presence or absence of sedimentation of pigment as storage stability, and viscosity change. The cartridge of HG5130 was filled and printing was performed, and the state of clogging was observed.

[Average Particle Size] Photon correlation spectroscopy particle size distribution meter (Coulter Electronics Co., Ltd.
Measured in 4).

[Storage Stability] 30 cc of the recording liquid was placed in a screw cap bottle and allowed to stand at 60 ° C. for 1 month. Then, the presence or absence of sedimentation of the pigment was examined and the viscosity was measured with a B-type viscometer (Tokyo Keiki Co., Ltd.).
The viscosity at 5 ° C. was measured. No pigment settling 〇 Pigment settling × No viscosity change 〇 Slightly thickening △ Thickening ×

[Discharge Stability] The ejection was continuously carried out for 1 hour, and the presence or absence of clogging was examined. No clogging occurred 〇 Clogged within 15 to 30 minutes after launch △ Clogged within 15 minutes after launch ×

The evaluation results are shown in the table below. ─────────────────────────────────── Recording liquid pigment treatment solvent Particle size Pigment precipitation viscosity change Discharge type Dispersion Stability of agent with or without nm drop ────────────────────────────────── Example 1 a IB * 105 〇 〇 〇 Example 2 b IB 110 〇 〇 〇 Example 3 c IB 120 〇 〇 〇 Comparative Example 1 200 × △ × Example 4 d DEG ** 105 〇 〇 〇 Example 5 e DEG 102 〇 〇 〇 Comparative Example 2 160 △ △ × Example 6 f IB 150 〇 〇 〇 Comparative Example 3 450 × × × Example 7 a IB 120 〇 〇 〇 Example 8 c IB 130 〇 〇 〇 Comparative Example 4 350 × × × Example 9 b IB 95 〇 〇 〇 Example 10 c IB 100 〇 〇 〇 Comparative Example 5 250 × Δ × Example 11 g DEG 9 〇 〇 〇 Comparative example 6 200 × Δ × Example 12 a IB 90 〇 〇 〇 Comparative example 7 220 Δ Δ × Example 13 b DEG 120 〇 〇 〇 Comparative example 8 300 × Δ × Example 14 f IB 100 〇 〇 Comparative Example 9 230 × × × ────────────────────────────────── * Isobutanol ** Diethylene glycol

[0076]

According to the present invention, the dispersibility of the pigment dispersion type,
It has become possible to obtain an inkjet recording liquid having excellent ejection stability.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuharu Iida 2-13-13 Kyobashi, Chuo-ku, Tokyo Inside Toyo Ink Manufacturing Co., Ltd.

Claims (9)

[Claims] 1. An inkjet recording liquid comprising a colorant dispersed in an aqueous liquid, wherein a solution of an organic pigment dissolved in sulfuric acid as the colorant is thrown into water to form fine precipitates, An inkjet recording liquid comprising a pigment obtained by treating a lower alcohol having 1 to 5 carbon atoms at 40 to 200 ° C. in the presence of a pigment dispersant. 2. The ink jet recording liquid according to claim 1, wherein a solution prepared by dissolving an organic pigment in sulfuric acid is thrown into continuously flowing water. 3. The ink jet recording liquid according to claim 1 or 2, further comprising an aqueous resin. 4. The organic pigment is a quinacridone pigment, a phthalocyanine pigment, a benzimidazolone pigment, a diketopyrrolopyrrole pigment, a perinone pigment, an anthraquinone pigment, a dioxazine pigment, a perylene pigment, an isoindolinone pigment. The ink jet recording liquid according to any one of claims 1 to 3, which is one kind selected from the group consisting of pigments. 5. The pigment dispersant is one of the following general formulas (1) and (2):
5. The inkjet recording liquid according to claim 1, which is at least one of the compounds represented by (3) and (3). Formula (1) P- (X- (CH 2) n -N (R 1) R 2 ] _m Formula (2) P- [X- (CH _{2) n} -Y] _m Formula (3) P -(SO ₃ H) _m (wherein P is an organic dye residue or a heterocyclic residue, X is
Is SO ₂ NH or CONH, Y is SO ₃ H or C
OOH, R ¹ and R ² each independently form an optionally substituted alkyl group having 1 to 18 carbon atoms or R ¹ and R ² to form a heterocyclic ring which may have a substituent. Well,
n represents an integer of 1 to 6 and m represents an integer of 1 to 3. ] 6. The ink jet recording liquid according to claim 1, which is filtered with a filter having a pore diameter of 1 μm or less. 7. The solid content of the colorant is 0.1 to 10% by weight.
7. The water-dispersed inkjet recording liquid according to any one of claims 1 to 6, further comprising: 8. A viscosity of 0.8 to 15 mPa · s (25
C.) The water-dispersed inkjet recording liquid according to claim 1. 9. A solution of an organic pigment dissolved in sulfuric acid is poured into water to form a fine precipitate, which is then treated in a lower alcohol having 1 to 5 carbon atoms at 40 to 200 ° C. in the presence of a pigment dispersant. A method for producing a water-dispersible inkjet recording liquid, which comprises adding water to a concentrated aqueous dispersion containing a pigment and an aqueous resin to dilute the mixture, and filtering the mixture with a filter having a pore size of 1 μm or less.