JP2001139863A - Method for manufacturing recording liquid for ink jet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a water-dispersed recording liquid for an ink jet recording excellent in water resistance and transparency and good in jetting stability at a nozzle. SOLUTION: The method for preparing a water-dispersed recording liquid for ink jet recording comprises the following steps (a) to (d): a step (a) for micronizing an organic pigment (A) by mechanically kneading a mixture comprising at least three components, the organic pigment (A), a water-soluble inorganic salt (B) and a water-soluble solvent (C), a step (b) for obtaining an aqueous dispersion of the organic pigment (A) having an average particle size of 10-150 nm (a measured value by a laser scattering method) by washing out the water- soluble inorganic salt (B) and the watersoluble solvent (C) from the mixture containing the micronized organic pigment (A), a step (c) for adding a water- based resin to the aqueous dispersion and dispersing it, and a step (d) for diluting the resultant dispersion by adding water and an additive and filtering it with a filter having a pore size of 3 μm or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a recording liquid for ink-jet recording which is excellent in water resistance, transparency and projection stability from a nozzle.

[0002]

2. Description of the Related Art Conventionally, an ink jet recording liquid has been prepared by dissolving a water-soluble dye such as an acid dye, a direct dye or a basic dye in a glycol solvent and water (Japanese Patent Application Laid-Open No.
No. 1412, JP-A-54-89811 and JP-A-55-65269) are often 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, ink jet recordings generally have poor water resistance,
If water is spilled, there is a problem in that bleeding by a dye easily occurs in a recording portion.

In order to improve such poor water resistance,
Attempts have been made to change the structure of the dye or to prepare a recording solution having a strong basicity (JP-A-56-57862). It has also been attempted to improve the water resistance by making good use of the reaction between the recording paper and the recording liquid (Japanese Patent Application Laid-Open No. 50-1980).
No. 49004, JP-A-57-36692, JP-A-59-20696, and JP-A-59-14688.
No. 9). These methods have a significant effect on certain recording papers. However, it lacks versatility in that it is limited by the recording paper, and when a recording paper other than a specific recording paper is used, the recording liquid using a water-soluble dye cannot provide sufficient water resistance of the recorded material. There are many.

[0004] 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. However, these recording liquids are problematic in terms of the odor of the solvent and the discharge of the solvent, and are not environmentally preferable. In addition, there is a problem that, for example, when a large amount of recording is performed or where the apparatus is installed, it is necessary to collect a solvent.

In order to improve the water resistance of the recorded matter, a recording liquid in which a pigment is dispersed in an aqueous medium has been developed. However, in the recording liquid for ink jet, the nozzle diameter is becoming narrower as the high resolution of the printer is desired, and accordingly, the particle diameter of the colorant needs to be made finer. Further, there is a demand for transparency on a par with dyes in forming an image on a transparent base material such as an overhead projector, and miniaturization is also demanded from the viewpoint of pigment coloring.

In general, the transparency of paints, inks, and the like improves as the degree of dispersion is increased by reducing the particle size of the pigment. However, in a usual dispersing machine such as a sand mill, a three-roll mill, and a ball mill, if the primary particles are dispersed, the transparency cannot be further improved. This is because the dispersing process in a usual dispersing machine mainly involves only breaking the secondary particles into primary particles, and it is necessary to further reduce the primary particles in order to further improve the transparency. In a high-speed sand mill,
In some cases, the primary particles can be made finer depending on the pigment used. However, it is practically difficult to make the primary particles finer even with a very large amount of energy.

As a means for making the primary particles fine, a method is known in which a pigment dissolved in a strong acid such as concentrated sulfuric acid or polyphosphoric acid is poured into cold water to precipitate the pigment as fine particles. However, in this method, usable pigments are significantly limited in terms of solubility and stability of the pigment in strong acids.
In addition, since the pigment finely divided by this method causes strong secondary aggregation when dried, it is very difficult to re-disperse the dried pigment to primary particles. As another method, there is also known a method in which a pigment and a solid resin are heated and kneaded with a two-roll or Banbury mixer while being heated. However, since pigments generally grow at high temperatures, this method ends when the mechanical crushing force and crystal growth reach an equilibrium state, and there is a limit to the fineness of the pigment.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the conventional method, and provides a method for producing a water-dispersed ink-jet recording liquid having excellent water resistance, transparency, and good projection stability at a nozzle. The purpose is to provide.

[0009]

The present invention comprises the following step a).
(A) Organic pigment (A), water-soluble inorganic salt (B) three times or more of organic pigment (A) and water-soluble solvent (C) B) mechanically kneading a mixture consisting of at least three components to micronize the organic pigment (A); b) water-soluble inorganic salt (B) and water-soluble inorganic pigment (B) from the micronized mixture of organic pigment (A) Washing the water-soluble solvent (C) with water to obtain an aqueous dispersion of the organic pigment (A) having an average particle diameter of 10 to 150 nm (measured by laser scattering); c) adding an aqueous resin to the aqueous dispersion to disperse it; D) a step of diluting the dispersion by adding water and additives thereto, and filtering the resultant through a filter having a pore size of 3 μm, preferably 1 μm or less.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, in order to obtain transparency of a water-dispersed inkjet recording liquid and a recorded matter using the same, an inorganic salt is used as a crushing aid, and primary particles of an organic pigment are mechanically dispersed. A finely divided material (this step is hereinafter referred to as salt milling) is used as a coloring agent. Further, at this time, by using the pigment derivative (D) together, the present invention provides an ink jet recording liquid which gives a printed matter which is transparent and excellent in water resistance.

The above-mentioned salt milling method will be described more specifically. Organic pigment (A) and organic pigment (A) 3
A mixture comprising at least three times the amount of the water-soluble inorganic salt (B) and the water-soluble solvent (C) and a pigment derivative (D) represented by the formula (1) if necessary is converted into a clay-like mixture, After thoroughly kneading with a kneader or the like, the mixture is poured into water and stirred with a high-speed mixer to form a slurry. Next, the slurry is repeatedly filtered and washed with water,
The water-soluble inorganic salt (B) and the water-soluble solvent (C) are removed. The resin (E) which is solid and water-insoluble at room temperature may be used in combination. By this method, the organic pigment (A) is miniaturized, and an aqueous dispersion of the organic pigment (A) having an average particle diameter of 10 to 150 nm (measured by laser scattering) can be obtained.

Further, the pigment derivative (D) is replaced with an organic pigment (A)
When used together, a pigment treated with the pigment derivative (D) (hereinafter also referred to as a treated pigment) is obtained. When the resin (E) which is solid and water-insoluble at room temperature is used together with the organic pigment (A), a pigment treated with the water-insoluble resin (E) (hereinafter also referred to as a treated pigment) is obtained.

The organic pigment (A) is miniaturized, and an aqueous dispersion of the organic pigment (A) or an aqueous dispersion of the treated pigment having an average particle size of 10 to 150 nm (measured by laser scattering) is used to color an ink jet recording liquid. Used as an agent. This aqueous pigment dispersion is a dispersion of fine particles. However, in order to prepare a recording liquid for ink jet, a stable dispersion is obtained by dispersing the aqueous resin or dispersant and the like further with a disperser. This dispersion is achieved by dispersing with an ordinary dispersing machine such as a sand mill, so that the pigment is finer and more stable than when untreated pigment (not subjected to salt milling treatment) is used. The recording liquid for use can be easily obtained in a short time without greatly increasing the dispersion time.

The pigment used in the present invention is not particularly limited as long as it does not dissolve in water. However, it is generally difficult to make the primary particles of the pigment finer for inorganic pigments whose hardness is higher than or less than that of the inorganic salt of the crushing aid. Therefore, it is preferable to use an organic pigment having a low hardness. However, inorganic pigments such as barium sulfate and silica which are generally used as an extender may be used together during salt milling or during subsequent dispersion.

Examples of the organic pigment (A) used in the present invention include quinacridone-based organic pigments, phthalocyanine-based organic pigments, benzimidazolone-based organic pigments, isoindolinone-based organic pigments, and azo-based organic pigments. The organic pigment (A) is described in more detail as follows. Toluidine Red, Toluidine Maroon, Hansa Yellow,
Insoluble azo pigments such as benzidine yellow and pyrazolone red; soluble azo pigments such as litol red, helio bordeaux, pigment scarlet and permanent red 2B; derivatives from vat dyes such as alizarin, indanthrone, and thioindigo maroon; phthalocyanine blue; Phthalocyanine series such as phthalocyanine green,
Quinacridones such as quinacridone red and quinacridone magenta; perylenes such as perylene red and perylene scarlet; isoindolinones such as isoindolinone yellow and isoindolinone orange; pyranthrones such as pyranthrone red and pyranthrone orange; thioindigo System, condensed azo system, benzimidazolone system and other pigments such as flavanthrone yellow, acylamide yellow, quinophthalone yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine Violet etc.

Such a pigment is referred to as a color index (C.
I) The following is a more specific example using numbers. CI Pigment Yellow 12, 13, 14, 17, 2
0, 24, 74, 83, 86, 93, 109, 110,
117, 125, 137, 138, 147, 148, 1
53, 154, 166, 168, CI Pigment Orange 16, 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 48, 49, 52, 53, 57, 9
7, 122, 123, 149, 168, 177, 18
0, 192, 215, 216, 217, 220, 22
3, 224, 226, 227, 228, 238, 24
0, CI Pigment Violet 19, 23, 29, 3
0, 37, 40, 50, CI Pigment Blue 15, 1
5: 1, 15: 4, 15: 6, 22, 60, 64, CI
Pigment Green 7, 36, CI Pigment Brown 23, 25, 26, and the like.

The water-soluble inorganic salt (B) used in the present invention
Examples thereof include sodium chloride and potassium chloride. These inorganic salts are used for miniaturizing the organic pigment (A), and commercially available salt or the like is pulverized by a pulverizer and used. In order to miniaturize the organic pigment (A), it is necessary to use at least 3 times by weight of these inorganic salts with respect to the organic pigment (A). If it is less than 3 times by weight, the desired particle size cannot be obtained. The upper limit is not particularly limited, but is 20 times by weight or less, preferably 10 times by weight or less. Even if the above upper limit is exceeded, there is a problem that a large amount of cleaning treatment is performed in a subsequent step, and a substantial amount of the organic pigment (A) is reduced.

The water-soluble solvent (C) used in the present invention
Is used as a wetting agent during salt milling, and is not particularly limited as long as it is water-soluble. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a solvent having a high boiling point is preferred from the viewpoint of safety. The water-soluble solvent (C) is generally used in an amount of 0.5 to the organic pigment (A).
Used up to 10 times by weight. When the amount is less than the lower limit of the above range, the kneading of the mixture of the organic pigment and the water-soluble inorganic salt becomes too large, and the kneading is substantially difficult. Exceeding the upper limit is not preferred because the mixture becomes almost liquid and no shear is applied during kneading, and the organic pigment cannot be miniaturized.

For example, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, diethylene glycol Propylene glycol monoethyl ether, low molecular weight polypropylene glycol and the like are used.

The pigment derivative (D) used in the present invention is a derivative of an organic dye, and a substituent is added to P in the following formula (1), that is, a residue of the organic dye to obtain an organic pigment (A).
Is a derivative effective for dispersion of

P- [XYZN (R ¹ ) R ² ] n (1) (where P is an organic dye residue, X is —SO ₂ —,
_{-CO -, - CH 2 -,} - CH 2 S -, - CH 2 O -, -
O -, - COO -, - NH -, - CH 2 NHCOCH-
At least one divalent linking group selected from the group consisting of: Y is a direct bond, -NR- (where R is H or an alkyl group having 1 to 18 carbon atoms), a divalent linking group selected from -O-, Z May be an alkylene group having 1 to 6 carbon atoms, R ¹ and R ² may be each independently an alkyl group having 1 to 18 carbon atoms which may be substituted, or may form a heterocyclic ring with R ¹ and R ^2. Often, the heterocyclic ring may have a substituent, and n is 1 to
P in the formula (1), that is, as the organic dye residue,
Examples include azo, phthalocyanine, quinacridone, benzimidazole, anthraquinone, perylene, perinone, thioindigo, dioxazine, isoindolinone, quinophthalone, triphenylmethane, and metal complex salts.

The organic pigment (A) and the pigment derivative (D)
In P, ie, the organic dye residue, it is usually preferable to combine the same dyes from the viewpoint of hue. For example, a phthalocyanine-based residue is used for a blue pigment, a quinacridone-based residue is used for a red pigment, and a benzimidazole-based residue is used for a yellow pigment.
However, they do not necessarily need to be the same system.

The substituent added to the organic dye residue P is represented by-[XYZN (R1) R2] n. X represents —SO ₂ —, —CO—, —CH ₂ —, —CH _{2
S -, - CH 2 O -} , - O -, - COO -, - NH-,
—CH ₂ NHCOCH— is at least one divalent linking group. Preferably, -SO _2- , -CO
—, —CH ₂ — and the like. Y is a direct bond or -N
(R)-(where R is H or an alkyl group having 1 to 18 carbon atoms) or -O-. Z may form a heterocyclic ring with an alkylene group having 1 to 6 carbon atoms, or R ¹ and R ^2, and N, O,
S. The heterocyclic ring may have a substituent. n represents an integer of 1 to 3.

The number (n) of the substituents added to the organic dye residue P is 1 to 3, and specific examples thereof include the following substituents.

[0025]

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It is desirable that these pigment derivatives (D) are partially soluble in a water-soluble solvent used as a wetting agent during salt milling. When the pigment derivative is not soluble, the pigment derivative may be made soluble by adding a dilute acid and neutralizing the pigment derivative. Acetic acid, hydrochloric acid, sulfuric acid and the like can be used as such an acid. Salt milling can also be performed using a pigment derivative that is liquid at room temperature. In addition, salt milling can be performed by using two or more kinds of derivatives in combination. At that time, a partially liquid derivative may be used.

The pigment derivative (D) which can be used in the present invention is 1 part by weight based on 100 parts by weight of the organic pigment (A).
It is desirable to use 50 to 50 parts by weight. When the amount is less than 1 part by weight, the coating effect is small, and the dispersion stability of the recording liquid over time is lacking. On the other hand, when the amount is more than 50 parts by weight, the dispersion stability of the organic pigment (A) is rather reduced, and the printed matter is poor. It is not preferable because resistance is lowered.

As the resin (E) which is solid and water-insoluble at room temperature which can be used in the present invention, in addition to a pure synthetic polymer,
It includes semi-synthetic polymers such as cellulose derivatives, rubber derivatives and protein derivatives, natural polymers such as rosin, and oligomers thereof. However, it must be solid at room temperature, insoluble in water, and soluble in a water-soluble solvent used as a wetting agent during salt milling. Salt milling can also be performed using two or more polymers in combination. In this case, a partially liquid polymer may be used. Among these resins, rosin epoxy resin and (meth) acrylic resin are particularly versatile, and rosin-modified maleic acid resin, rosin-modified phenol resin and the like are used. In addition, these have a large effect of salt milling.

In the present invention, the epoxy resin used at the time of salt milling refers to an epoxide containing one or more epoxy groups in a molecule, and an epoxy resin cross-linked with a curing agent generally has almost no solubility, and Since it hardly dissolves in (C), it is not used in the present invention. As the epoxide, bisphenol type, novolak type, alkylphenol type, resorcinol type, polyglycol type, ester type, glycidyl type such as N-glycidylamine, and cycloaliphatic epoxide are used.

The (meth) acrylic resin used at the time of salt milling in the present invention may be a copolymer of acrylic acid and / or methacrylic acid and one or more acrylate and / or methacrylate monomers, and Copolymers with radically polymerizable monomers such as styrene, vinyl acetate, maleic anhydride and the like in an amount of not more than mol% are also included. However, a three-dimensionally crosslinked polymer, such as a copolymer with a polyfunctional monomer, has poor solubility and hardly dissolves in the above-mentioned water-soluble solvent (C), and thus is not suitable for the present invention.

The resin (E) which is solid and water-insoluble at room temperature and which can be used in the present invention is preferably used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the organic pigment (A).
When the amount is less than 10 parts by weight, the coating effect is small, and the dispersion stability of the recording liquid over time is lacking. On the other hand, when the amount is more than 50 parts by weight, the concentration of the recording liquid is reduced or the colorant is increased. It is not preferable because the viscosity increases and the ejection stability tends to decrease. In the salt milling step, in addition to the pigment derivative and a resin that is solid and water-insoluble at room temperature, additives such as a dispersant and a plasticizer may be used in combination, or two or more pigments may be mixed. It may be processed. The present invention is characterized in that an aqueous dispersion of an organic pigment subjected to the salt milling treatment as described above is used as a colorant without passing through a drying step to produce a recording liquid for inkjet.

The production of an ink jet recording liquid using an aqueous dispersion of the organic pigment (A) will be described below. The salt-milled organic pigment is converted to a water-containing material of about 80 to 50% by weight, mixed with a dispersant or an aqueous resin used for fixing, dispersed, and then further mixed with water, a wetting agent, an additive and the like. A method of adding the components, or kneading the hydrate of the organic pigment in advance with a water-based resin used for fixing with a dispersing machine such as a two-roll mill, and further mixing the kneaded product with water and, if necessary, other additives. A method of dispersing may be used.

In the present invention, the organic pigment is dispersed together with other components of the ink jet recording liquid in a state where the amount of the organic pigment is about 10 to 40% by weight for a short period of time, and thereafter, necessary for printing. It is preferable to employ a method of diluting the mixture so as to have an appropriate concentration, or a method of further dissolving the additive and filtering the solution.

The ink jet recording liquid according to the present invention uses the above-mentioned salt-milled organic pigment in an amount of 0.1 to 10 parts by weight as a solid content in 100 parts by weight of a water-dispersed ink jet recording liquid. Include an aqueous resin that contributes to fixability and dispersibility, a neutralizing agent for this aqueous resin, a dispersant for maintaining stable dispersion of organic pigments,
Aqueous solvent to maintain proper wettability of the recording liquid, antifungal agent to prevent the generation of mold and bacteria, surface tension, penetration regulator, chelating agent, antifoaming agent, etc. This is a recording liquid containing 50 to 98% by weight of water in the recording liquid.

Examples of the disperser used for producing the recording liquid containing the organic pigment subjected to the salt milling treatment include a sand mill, a homogenizer, a ball mill, a paint shaker, and an ultrasonic disperser. Dispersion is performed by a disperser or the like that disperses by a cavitation effect in a high-pressure room. Mixing and stirring can be performed by a high-speed disperser, emulsifier, or the like, in addition to stirring by a stirrer using a normal blade.

The mixed recording liquid may be used before dilution or
Thereafter, it is preferable to sufficiently filter with a filter having a pore size of 3 μm or less. Preferably, the filtration is performed with a filter having a size of 1.0 μm or less, more preferably 0.45 μm or less. Prior to filtration of the filter, by centrifugation
It is also possible to exclude those having a large particle size, thereby reducing clogging of the filter in filtration and prolonging the service life of the filter.

In the recording liquid of the present invention, since the organic pigment (A) is miniaturized, the particle diameter of the pigment in the recording liquid is as follows.
In the average particle size by laser scattering method, 10 to 150
nm, and preferably 10 to 100 nm as a recording liquid. Due to such a particle size, the filtration operation in the production of the recording liquid is easy, and the sedimentation of the recording liquid over time is small.

The aqueous resin that contributes to the fixing property and the dispersibility in the present invention includes a water-soluble resin soluble in water, a water-dispersible emulsion dispersed in water, and a colloidal dispersion resin. Used. Examples of such resins include water-soluble resins such as acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluorine-based resins, and water-dispersible emulsions or colloidal dispersion resins. Used. These aqueous resins are contained in the recording liquid in an amount of 0.5 to 10% by weight, preferably 1 to 5% by weight.
Used. If the amount is less than the lower limit of the above range, the coloring agent cannot be sufficiently fixed. On the other hand, if it exceeds the upper limit, the viscosity of the recording liquid is excessively increased and the ejection stability is undesirably reduced. When a water-soluble resin is used as the water-based resin, the viscosity of the recording liquid tends to be high, but the viscosity of the water-dispersible resin can be suppressed low, and the water resistance of the recorded matter can be increased. Can be improved. These resins may contain ammonia,
Add a neutralizing agent such as amine, inorganic alkali, etc.
The stability of dissolution or dispersion can be adjusted.

In the present invention, as an aqueous solvent used in addition to water, solidification of the recording liquid at the nozzle portion is prevented.
It is added as necessary to prevent stable jetting of the recording liquid and drying over time in the nozzle portion. Examples of such aqueous solvents include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether,
Ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone,
Examples thereof include 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like.

For the purpose of speeding up the drying of the recording liquid on paper, alcohols such as methanol, ethanol and isopropyl alcohol can be used. These aqueous solvents may be used alone or as a mixture of 0 to 50% of the recording liquid.
Used in the range. The water used as the recording liquid medium is ion-exchanged water or distilled water from which metal ions and the like have been removed.

When the recording liquid is to be printed on paper, a penetrant may be added to the recording liquid to stop the permeation of the recording liquid and to increase the apparent dryness. Examples of such penetrants include glycol ethers such as diethylene glycol monobutyl ether described as aqueous solvents, alkylene glycols, alkylene diols, polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, dioctylsulfosuccinic acid. Sodium and the like are exemplified. These have sufficient effects when the used amount of the recording liquid is 5% or less, and when the amount is more than 5%, printing bleeding and paper missing (print-through) occur, which is not preferable.

The recording liquid of the present invention may contain a fungicide to prevent the occurrence of mold. Examples of the fungicide include sodium dehydroacetate, sodium benzoate, sodium pyridinethione {1} oxide, zinc pyridinethione {1} oxide, 1,2-benzisothiazoline-3-one, and 1-benzisothiazoline-3-one. And the like. These are 0.0% of the recording liquid.
About 5 to 1.0% is used.

Further, a chelating agent can be added in order to prevent the deposition of metal at the nozzle portion and the deposition of insoluble matters in the recording liquid. The chelating agent blocks metal ions in the recording liquid. Specific examples of the chelating agent are as follows. Ethylenediaminetetraacetic acid, sodium salt of ethylenediaminetetraacetic acid, diammonium salt of ethylenediaminetetraacetic acid, tetraammonium salt of ethylenediaminetetraacetic acid, and the like.
The chelating agent is incorporated in the recording liquid in an amount of about 0.005 to 0.5% by weight.

Further, the pH of the recording liquid is adjusted to a desired pH, and amines, inorganic salts, and the like are used to ensure the stability of the recording liquid or the stability of the recording liquid piping in the recording apparatus, such as corrosion prevention.
A regulator such as ammonia and a buffer such as phosphoric acid may be blended in the recording liquid. In addition, an antifoaming agent can be added to the recording liquid in order to prevent the recording liquid from circulating or moving inside the pipe or inside the pipe, and from generating bubbles during the production of the recording liquid.

A surfactant can be used to maintain stable dispersion of the pigment, when the aqueous resin cannot be used for a dispersant, or for more stable dispersion. As such a surfactant, an anionic, nonionic, cationic, or zwitterionic surfactant can be used. Examples of anionic activators include fatty acid salts, alkyl sulfate salts, alkyl aryl sulfonates, alkyl naphthalene sulfonates,
Dialkyl sulfonate, dialkyl sulfosuccinate, alkyl diaryl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxy Examples include ethylene alkyl phosphate salts, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters.

Examples of the nonionic activator include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Non-ionic surfactants such as glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine-based, and silicon-based are exemplified.

Examples of the cationic activator include alkylamine salts, quaternary ammonium salts, alkylpyridinium salts, alkylimidazolium salts and the like.

Examples of the amphoteric activator include alkyl betaine, alkyl amine oxide, phosphadyl choline and the like.

For the purpose of adjusting the hue of the pigment, imparting a concentration, etc., a dye can be used in such a form that there is no problem in water resistance and light resistance. Depending on the use of the dye, the dispersion stability of the pigment may be deteriorated. Therefore, it is necessary to limit the use of the pigment to 40% by weight or less, preferably 25% by weight or less. As the dye, a disperse dye, a water-insoluble dye of an oil-soluble dye, a direct dye, an acid dye, a basic dye, a reactive dye, a metal-containing dye, and the like are used. These dyes are preferably purified dyes from which inorganic salts have been removed.

Specifically, C.I. I. Direct black 17, 19, 32, 51, 71, 108, 146, 15
4,166, C.I. I. Add Black 2,7,24,2
6, 31, 52, 63, 112, 118, C.I. I. Basic Black 2, C.I. I. Direct Blue 6,2
2, 25, 71, 90, 106, C.I. I. Acid Blue 9, 22, 40, 59, 93, 102, 104, 11
3, 117, 120, 167, 229, 234, C.I.
I. Basic Blue 1,3,5,7,9,24,2
5, 26, 28, 29, C.I. I. Direct Red 1,
4, 17, 28, 83, C.I. I. Acid Red 1,
6,32,37,51,52,80,85,87,9
2,94,115,180,256,315,317.
C. I. Basic Red 1,2,9,12,13,1
4, 37, C.I. I. Direct Yellow 12, 24, 2
6,98, C.I. I. Acid Yellow 11, 17, 23,
25, 29, 42, 61, 71, C.I. I. Basic yellow 11, 28. C. I. Direct orange 34,3
9, 44, 46, 60, C.I. I. Direct Violet 47, 48, C.I. I. Direct Brown 109,
C. I. Direct Green 59, C.I. I. Acid Orange 7, 19, C.I. I. Acid violet 49,
C. I. Basic violet 7, 14, 27 and the like are exemplified.

As other additives, urea, dimethyl urea and the like can be added. The recording liquid is preferably adjusted as a liquid having a viscosity of 0.8 to 15 cps (25 ° C.), depending on the type of the recording apparatus. Surface tension is 25-6
The pH is preferably 0 dyn / cm, and the pH is not particularly limited, but is in the range of 4 to 12, and the alkalinity of 7 to 10 is preferable.

[0052]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments. Parts and% in the examples indicate parts by weight and% by weight, respectively.

[0053]

Example 1-1: crude copper phthalocyanine (copper phthalocyanine manufactured by Toyo Ink Mfg. Co., Ltd.): 250 parts, sodium chloride: 2500 parts, and polyethylene glycol 300
(Tokyo Kasei Co., Ltd.): 160 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 4 hours. Next, the mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and then filtered and washed with water 5 times to repeat sodium chloride and solvent. And an aqueous pigment dispersion having a solid content of 50% (treated pigment dispersion) was obtained. The following materials were placed in a sand mill and dispersed for 4 hours to prepare a concentrated recording liquid for inkjet.

Blue pigment (treated pigment dispersion, solid content 50%) 30.0 parts Acrylic resin aqueous solution (Johncryl 62, manufactured by Johnson Polymer Co., 34.6% solid content) 3.0 parts Dispersant (Kao Corporation, “Emulgen”) 420 ") 2.0 parts Purified water 50.0 parts Glycerin 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording solution.

The above dispersion 13.5 parts Dispersant (“Emulgen 420” manufactured by Kao Corporation) 0.2 part Acrylic resin aqueous solution 3.0 parts (“Emapoly TYN-40” solid content 44.8% manufactured by Gifu Shellac Manufacturing Co.) Ethylene Glycol 30.0 parts Antifungal agent ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 part Purified water 63.53 parts Filterability when obtaining a recording liquid was evaluated. The viscosity and average particle diameter of the obtained recording liquid were evaluated as described below, and the jetting characteristics, printing state, transparency of the recorded matter, water resistance of the recorded matter, and the like were evaluated when the recording liquid was used. . Table 1 shows the results
To Table 4 below. [Filterability] The amount that could be filtered through a 1 μm and 0.45 μm membrane filter with a diameter of 90 mm within a certain period of time. [Viscosity] The viscosity was measured at 25 ° C using a B-type viscometer. [Average Particle Size] The average particle size was measured by a laser scattering type particle size distribution meter (“DLS-700” manufactured by Otsuka Electronics Co., Ltd.). [Printing state] This recording liquid was applied to Epson HG5130.
And recorded on plain paper. The printed state of the recorded matter was visually evaluated. [Ejection Characteristics] The ejection state of the nozzles during continuous printing was evaluated based on the printed matter. Good: Continuous printing was accurately performed at a predetermined position. Defective: Despite continuous printing, a defect occurs on the way, or printing is not performed at a predetermined position. [Water resistance] In the case of recording on plain paper, dripping water on the recording surface, or drying the printed matter, visually check the presence or absence of ink bleeding and ink flow when immersed in water for 1 minute. evaluated. [Transparency] Transparency when the ink was spread on an OHP sheet for inkjet using a 1.5 mil applicator was visually evaluated.

[0056]

Example 1-2 Crude copper phthalocyanine (copper phthalocyanine manufactured by Toyo Ink): 250 parts, sodium chloride:
2500 parts, a blue pigment dispersant (P- [CH2NH (C
H2) 4N (CH3) 2] 3, P is a copper phthalocyanine residue) 25 parts and polyethylene glycol 300
(Tokyo Kasei Co., Ltd.): 160 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, the mixture was poured into 2.5 liters of warm water,
The slurry was stirred for about 1 hour with a high-speed mixer while being heated to 0 ° C., and then filtered and washed five times to remove sodium chloride and the solvent. Pigment dispersion).
The following materials were placed in a sand mill and dispersed for 3 hours to prepare a concentrated recording liquid for inkjet.

Blue pigment (pigment derivative-treated pigment dispersion 50% product) 30.0 parts Acrylic resin aqueous solution (“Johncryl 61J” solid content: 31.0%, manufactured by Johnson Polymer) 3.0 parts Dispersant (Kao Corporation “Emulgen”) 420 ") 1.0 part Purified water 50.0 parts Glycerin 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording solution.

The above dispersion 13.5 parts Dispersant (“Emulgen 420” manufactured by Kao Corporation) 0.2 parts Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd., solid content 30%) 1.0 part Ethylene glycol 10 0.0 parts Antifungal agent ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Purified water 63.53 parts

[Reference Example 1] Crude copper phthalocyanine (manufactured by Toyo Ink Co., Ltd.)
Copper phthalocyanine): 250 parts, sodium chloride: 25
00 parts, 90 parts of Epicoat 1004 (manufactured by Yuka Shell Epoxy, epoxy resin) and 160 parts of polyethylene glycol 300 (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. . Next, the mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and filtered and washed with water for 5 hours.
An aqueous pigment dispersion (epoxy-treated pigment dispersion) having a solid content of 50% by repeatedly removing sodium chloride and the solvent.
I got The following materials are put in a sand mill and dispersed for 3 hours.
A concentrated recording liquid for inkjet was prepared.

Blue pigment (Epoxy-treated pigment dispersion, solid content 50%) 30.0 parts Acrylic resin aqueous solution (Johncryl 61J, manufactured by Johnson Polymer Co., 31.0% solid content) 3.0 parts Dimethylaminoethanol 0.1 part Dispersant (“Emulgen 420” manufactured by Kao Corporation) 1.0 part Purified water 50.0 parts Glycerin 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording solution.

The above dispersion 13.5 parts Dispersant (“Emulgen 420” manufactured by Kao Corporation) 0.2 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd., solid content 30%) 1.0 part Ethylene glycol 10 0.0 parts Antifungal agent ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Purified water 63.53 parts

[0061]

Example 2-1 In place of crude copper phthalocyanine of Example 1-1, 260 parts of a yellow pigment ("Poster Palm Yellow H3G" manufactured by Hoechst) was used. Pigment dispersion). Thereafter, the mixture was dispersed in a sand mill for 5 hours to obtain an inkjet recording liquid having excellent transparency and water resistance in the same manner as in Example 1 except that a concentrated recording liquid for inkjet was prepared. The evaluation results are shown in Tables 1 to 4.

[0062]

EXAMPLE 2-2 In place of the crude copper phthalocyanine of Example 1-2, 260 parts of a yellow pigment ("Poster Palm Yellow H3G" manufactured by Hoechst) was used, and instead of the blue pigment dispersant, a yellow pigment dispersant ( P- [CH2NH (CH2)
Using 15 parts of 4N (CH3) 2] 3 and P for a benzimidazole residue, the same treatment as in Example 1 was carried out to obtain an ink jet recording liquid having excellent transparency and durability.
The results are shown in Tables 1 to 4.

[0063]

Reference Example 2 Instead of the crude copper phthalocyanine of Reference Example 1, a yellow pigment ("Poster Palm Yellow H" manufactured by Hoechst) was used.
An aqueous pigment dispersion (treated pigment dispersion) was obtained in the same manner as in Example 1 using 260 parts of 3G ″). Thereafter, the mixture was dispersed by a sand mill for 4 hours to prepare a concentrated recording liquid for inkjet. An ink jet recording liquid having excellent transparency and water resistance was obtained in the same manner as in Example 1. The evaluation results are shown in Tables 1 to 4.

[0064]

Example 3-1 250 parts of crude copper phthalocyanine (copper phthalocyanine manufactured by Toyo Ink Mfg. Co., Ltd.), 900 parts of sodium chloride, and 160 parts of diethylene glycol (manufactured by Tokyo Kasei) were charged into the kneader described in Example 1, and 5
Kneaded for hours. This was treated in the same manner as in Example 1 to obtain a solid content of 5%.
An aqueous dispersion of 0% of the treated pigment was obtained. The following materials were placed in a sand mill and dispersed for 4 hours to prepare a concentrated recording liquid for inkjet.

Blue pigment (50% treated pigment dispersion) 30.0 parts Acrylic resin emulsion (Nippon Polymer “F-157” solid content 30%) 1.3 parts Dispersant (Zeneca “Solsperse 27000”) 0.5 part) Purified water 74.0 parts Glycerin 5.8 parts Dimethylethanolamine 0.1 part After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered with a 3 μm membrane filter, subsequently with a 1 μm membrane filter, and subsequently with a 0.45 μm filter to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 25.0 parts Glycerin 20.0 parts Antifungal agent (“Sodium Omazine” manufactured by Nippon Orin Co., Ltd.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Diethylene glycol monobutyl ether 0.5 Part Silicon emulsion type water-based defoaming agent (Kao Corporation "Anti-Home E-20") 0.8 part

[0067]

Example 3─2 250 parts of crude copper phthalocyanine (copper phthalocyanine manufactured by Toyo Ink Mfg. Co., Ltd.), 900 parts of sodium chloride, blue pigment dispersant (P- [CH 2 NH)
(CH2) 4N (CH3) 2] 3, P is a copper phthalocyanine residue (25 parts), Joncryl 682 (an acrylic oligomer manufactured by Johnson Wax): 100 parts, and diethylene glycol (manufactured by Tokyo Chemical Industry): 160 parts. The kneader described in 1 was charged and kneaded for 2 hours. This was subjected to the same operation as in Example 1 to obtain a pigment derivative-treated pigment aqueous dispersion having a solid content of 50%.

The following materials were placed in a sand mill and dispersed for 4 hours to prepare a concentrated recording liquid for inkjet. Blue pigment (50% pigment derivative-treated pigment dispersion) 30.0 parts Acrylic resin emulsion (Nippon Polymer "F-157" solid content 30%) 1.3 parts Dispersant (Zeneca "Solsperse 27000") 0.5 part Purified water 74.0 parts Glycerin 5.8 parts Dimethylethanolamine 0.1 part After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered with a 3 μm membrane filter, subsequently with a 1 μm membrane filter, and subsequently with a 0.45 μm membrane filter to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 25.0 parts Glycerin 20.0 parts Antifungal agent (“Sodium Omazine” manufactured by Nippon Olin Co.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Diethylene glycol monobutyl ether 0.5 Part Silicon emulsion type water-based defoamer (Kao Corporation "Anti-Home E20") 0.8 part

Reference Example 3 250 parts of crude copper phthalocyanine (copper phthalocyanine manufactured by Toyo Ink Mfg. Co., Ltd.), sodium chloride: 9
In a kneader described in Example 1, 100 parts, 100 parts of John Krill 682 (acrylic oligomer manufactured by Johnson Wax) and 160 parts of diethylene glycol (manufactured by Tokyo Kasei) were charged and kneaded for 2 hours. This was treated in the same manner as in Example 1 to obtain an aqueous dispersion of an acrylic-treated pigment having a solid content of 50%. The following materials were placed in a sand mill and dispersed for 3 hours to prepare a concentrated recording liquid for inkjet.

Blue pigment (Acrylic-treated pigment dispersion 50% product) 30.0 parts Acrylic resin emulsion (Nippon Polymer Co., Ltd. “F-157” solid content 30%) 1.3 parts Aqueous ammonia 10% 0.3 parts Dispersion 0.5 part of purified agent (“Solsperse 27000” manufactured by Zeneca) 74.0 parts of purified water 5.8 parts of glycerin 0.1 part of dimethylethanolamine After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered with a 3 μm membrane filter, subsequently with a 1 μm membrane filter, and subsequently with a 0.45 μm filter to produce a recording solution.

The above dispersion 25.0 parts Glycerin 10.0 parts Fungicide (“Sodium Omazine” manufactured by Nippon Orin Co., Ltd.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Diethylene glycol monobutyl ether 0.5 parts Silicon 0.8 parts of emulsion type water-based defoaming agent (“Kaosha Anti-Home E20”)

[0072]

Example 4-1 Red pigment ("Poster Palm Pink E" manufactured by Hoechst): 250 parts, sodium chloride: 250
0 parts, polyethylene glycol 300 (manufactured by Tokyo Chemical Industry Co., Ltd.): 160 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, this mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and then filtered and washed with water five times to repeat sodium chloride and solvent. And an aqueous pigment dispersion having a solid content of 50% (treated pigment dispersion) was obtained. The following materials were placed in a paint shaker and dispersed for 4 hours to prepare a concentrated recording liquid for inkjet.

Red pigment (50% treated pigment dispersion) 30 parts Aqueous acrylic resin ("Johncryl 62" manufactured by Johnson Polymer Co., 34.6% solid content) 3.0 parts Dispersant ("Emulgen A-90" manufactured by Kao Corporation) 1.0 part) Purified water 50.0 parts Glycerin 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently filtered through a 0.45 μm filter to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 13.5 parts Dispersant (“Emulgen A-90” manufactured by Kao Corporation) 0.2 part Acrylic resin (“W-215” manufactured by Nippon Polymer Co., Ltd.) 1.0 part Ethylene glycol 10.0 parts Antifungal agent ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 part Sodium salt of ethylenediaminetetraacetylic acid 0.02 part Purified water 63.53 parts In addition to "HG5130" manufactured by Epson, this recording liquid was used as a fuze. When recording was performed in the cartridge of “thinkjet” manufactured by Red Packard, “Hink” manufactured by Epson
Good recorded matter was obtained as in the case of G5130 ″, and the water resistance was also sufficient.

[0075]

Example 4-2 Red pigment ("Poster Par" manufactured by Hoechst AG)
Mu Pink E "): 250 parts, sodium chloride: 250
0 parts, a red pigment dispersant (P- [CH_TwoNH (CH_Two)_FourN
(CH_Three) _Two]_Three, P is a quinacridone residue) 10 parts and
Polyethylene glycol 300 (Tokyo Kasei): 16
0 parts stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho)
And kneaded for 3 hours. The mixture is then added to 2.5
Put in liter of warm water and heat to about 80 ° C while heating.
Stir with a speed mixer for about 1 hour to form a slurry
Thereafter, filtration and washing were repeated 5 times, and sodium chloride and
Aqueous pigment dispersion having a solid content of 50% (pigment
Conductor-treated pigment dispersion) was obtained. The following ingredients in the sand mill
And dispersed for 4 hours to produce a concentrated recording solution for inkjet.
Made.

Red pigment (50% pigment dispersion treated with pigment derivative) 30.0 parts Acrylic resin aqueous solution (“Johncryl 62” solid content 31.0%, manufactured by Johnson Polymer Co.) 3.0 parts Dispersant (Kao Corporation “Emulgen”) A-90 ″) 1.0 part Purified water 50.0 parts Glycerin 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently filtered through a 0.45 μm membrane filter to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 13.5 parts Dispersant (“Emulgen A-90” manufactured by Kao Corporation) 0.2 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd., solid content 30%) 1.0 part Ethylene Glycol 10.0 parts Antifungal agent ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 parts Sodium salt of ethylenediaminetetraacetic acid 0.02 parts Purified water 63.53 parts In addition to "HG5130" manufactured by Epson, When this recording liquid was put into a cartridge of "thinkjet" manufactured by Hewlett-Packard Company, and recording was performed, Epson HG
As in the case of No. 5130, good recorded matter was obtained, and the water resistance was sufficient.

[0078]

REFERENCE EXAMPLE 4 In place of the crude copper phthalocyanine of Reference Example 1, 280 parts of a quinacridone pigment ("Poster Farm Pink E" manufactured by Hoechst) was used in the same manner as in Reference Example 1 to obtain excellent transparency and durability. Thus, an inkjet recording liquid was obtained. The evaluation results are shown in Tables 1 to 4. In addition to Epson's "HG5130", this recording liquid was put into a cartridge of Hewlett Packard's "thinkjet" and recording was performed.
As in the case of (1), good recorded matter was obtained, and the water resistance was sufficient.

[0079]

[Comparative Example 1] The following raw materials were placed in a paint shaker.
The mixture was dispersed for a time to prepare a concentrated recording liquid for inkjet.

Red pigment (Poster Palm Pink E, manufactured by Hoechst) 15.0 parts Acrylic resin aqueous solution (solid content: 34.6%, “Johncryl 62” manufactured by Johnson Polymer) 3.0 parts Dispersant (Emulgen, manufactured by Kao Corporation) A-90 ″) 1.0 part Purified water 50.0 parts Glycerin 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, the amount of filtration with a 1 μm membrane filter was significantly smaller than in Example 4. Further, since the filtration with a 0.45 μ filter was very difficult, the printing state, the ejection characteristics, and the like were not evaluated.

The above dispersion 13.5 parts Dispersant (“Emulgen A-90” manufactured by Kao Corporation) 0.2 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd., solid content 30%) 1.0 part Ethylene Glycol 10.0 parts Antifungal agent ("Sodium Omazine", manufactured by Nippon Olin Co.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Purified water 63.53 parts Even when dispersed for 8 hours, use a 1μ membrane filter. The amount of filtration was significantly smaller than that of Example 4. Also, 0.4
With a 5μ filter, filtration was very difficult.

[0082]

Example 5-1 Red pigment ("Poster Palm Pink E" manufactured by Hoechst): 250 parts, sodium chloride: 250
0 parts, polyethylene glycol 300 (manufactured by Tokyo Chemical Industry Co., Ltd.): 160 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 5 hours. Next, the mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and then filtered and washed eight times to obtain sodium chloride and a solvent. And an aqueous pigment dispersion having a solid content of 50% (treated pigment dispersion) was obtained. The following materials were placed in a sand mill and dispersed for 4 hours to prepare a concentrated recording liquid for inkjet.

Red pigment (treated pigment dispersion 50% product) 30.0 parts Acrylic resin aqueous solution (34.6% solid content “Johncryl 62” manufactured by Johnson Polymer Co.) 3.0 parts Dimethylaminoethanol 0.1 part Dispersant ( 1.0 part, purified water 50.0 parts, glycerin 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently filtered through a 0.45 μm membrane filter to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 13.5 parts Dispersant (“Emulgen A-90” manufactured by Kao Corporation) 0.2 parts Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd., solid content 30%) 1.0 part Ethylene Glycol 10.0 parts Antifungal agent ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Purified water 63.53 parts 2,4,7,9 {tetramethyl} 5 0.17 parts of decine 4,7 diol

[0085]

Example 5─2 Red pigment (“Poster Par” manufactured by Hoechst)
Mu Pink E "): 250 parts, sodium chloride: 250
0 parts, a red pigment dispersant (P- [CH_TwoNH (CH_Two)_FourN
(CH_Three) _Two]_Three, P is a quinacridone residue) 10 parts and
Polyethylene glycol 300 (Tokyo Kasei): 16
0 parts stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho)
And kneaded for 3 hours. The mixture is then added to 2.5
Put in liter of warm water and heat to about 80 ° C while heating.
Stir with a speed mixer for about 1 hour to form a slurry
Thereafter, filtration and washing were repeated 8 times, and sodium chloride and water were washed repeatedly.
Aqueous pigment dispersion having a solid content of 50% (pigment
Conductor-treated pigment dispersion) was obtained. The following ingredients in the sand mill
And dispersed for 4 hours to produce a concentrated recording solution for inkjet.
Made.

Red pigment (pigment derivative-treated pigment dispersion 50% product) 30.0 parts Acrylic resin aqueous solution (“Johncryl 62” solid content 31.0%, manufactured by Johnson Polymer Co.) 3.0 parts Dispersant (Kao Corporation “Emulgen”) A-90 ″) 1.0 part Purified water 50.0 parts Glycerin 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently filtered through a 0.45 μm membrane filter to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 13.5 parts Dispersant (“Emulgen A-90” manufactured by Kao Corporation) 0.2 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd., solid content 30%) 1.0 part Ethylene Glycol 10.0 parts Antifungal agent ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Purified water 63.53 parts

REFERENCE EXAMPLE 5 Instead of the crude copper phthalocyanine of Reference Example 3, 280 parts of a quinacridone pigment ("Poster Palm Pink E" manufactured by Hoechst) was used and treated in the same manner as in Reference Example 3. % Of an acrylic-treated pigment aqueous dispersion was obtained, and the following raw materials were placed in a sand mill and dispersed for 3 hours.

Red pigment (aqueous dispersion of quinacridone pigment treated with acryl at 50% solid content) 20.0 parts Acrylic resin aqueous solution (“PDX6101” solid content 40%, manufactured by Johnson Polymer) 2.8 parts Activator (manufactured by Kao Corporation) "Emulgen 420") 2.1 parts Purified water 74.5 parts Glycerin 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently filtered through a 0.45 μm membrane filter to produce a recording solution. The evaluation results are shown in Tables 1 to 4.

The above dispersion 13.5 parts Acrylic resin emulsion (Nippon Polymer Co., Ltd. "W-251" solid content 30%) 1.0 part Diethylene glycol 20.0 parts Antifungal agent (Zeneca "Proxel GXL") 0 .15 parts Ethylenediaminetetraacetic acid sodium salt 0.02 parts Dimethylaminoethanol 0.1 parts Purified water 63.53 parts

[0090]

Example 6-1 In the same manner as in Example 3 except that crude copper phthalocyanine of Example 3-1 was replaced with 280 parts of a yellow pigment ("Hanzabrilliant Yellow 9GX" manufactured by Hoechst), the solid content was reduced to 50%. An aqueous dispersion of the treated pigment was obtained.

The following raw materials were mixed and dispersed in a sand mill for 4 hours to prepare a concentrated recording liquid for inkjet.

Yellow pigment (aqueous dispersion of treated pigment having a solid content of 50%) 55.0 parts Acrylic resin aqueous solution (31.0% solid content "Johncryl 61J" manufactured by Johnson Polymer Co.) 7.0 parts Dispersant (manufactured by Kao Corporation) Emulgen A-90 ") 4.0 parts Purified water 56.0 parts Diethylene glycol monobutyl ether 3.0 parts N-methyl {2-pyrrolidone 3.0 parts 2,4,7,9-tetramethyl-5-decyne-4 1.0 part ethylene glycol 1.0 part After dispersing, mixing with the following, after mixing, filtration through a 1μ membrane filter, followed by filtration through a 0.45μ membrane filter, A recording liquid was produced. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 13.0 parts Dispersant (“SOLSPERS 27000” manufactured by Zeneca) 0.2 part Acrylic resin aqueous solution 3.0 parts (“Emapoly TYN-40” manufactured by Gifu Shellac Co., Ltd., solid content 44.8%) diethylamino Ethanol 0.2 parts Diethylene glycol 22.5 parts Antifungal agent (“Proxel GXL” manufactured by Zeneca) 0.15 parts Ethylenediaminetetraacetic acid sodium salt 0.02 parts Purified water 63.53 parts 2,4,7,9 0.1 parts of tetramethyl-5-decyne 4,7-diol

[0094]

Example 6-2 In place of the crude copper phthalocyanine of Example 3-2, 280 parts of a yellow pigment ("Hanza-Brillant Yellow 9GX" manufactured by Hoechst) was used, and a solid content of 50 was obtained in the same manner as in Example 3-2. % Of a pigment derivative treating agent aqueous dispersion. The following raw materials were mixed and dispersed in a sand mill for 2 hours to prepare a concentrated recording liquid for inkjet.

55.0 parts of yellow pigment (aqueous dispersion of acryl-treated pigment having a solid content of 50%) Acrylic resin aqueous solution (“Johncryl 61J” manufactured by Johnson Polymer Co., 31.0% solid content) 7.0 parts Dispersant (manufactured by Kao Corporation) "Emulgen A-90") 4.0 parts Purified water 56.0 parts Diethylene glycol monobutyl ether 3.0 parts N-methyl {2} pyrrolidone 3.0 parts 2,4,7,9-tetramethyl-5-tetracin- 4,7-diol 1.0 part Ethylene glycol 1.0 part After dispersing, mix with the following, mix and filter with 1μ membrane filter, then filter with 0.45μ membrane filter, record A liquid was produced. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 13.0 parts Dispersant (“Solsperse 27000” manufactured by Zeneca) 0.2 part Acrylic resin emulsion (“W-215” solid content 30%, manufactured by Nippon Polymer Co., Ltd.) 1.0 part Diethylene glycol 22. 5 parts Antifungal agent (“Proxel GXL” manufactured by Zeneca) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 part Purified water 63.53 parts 2,4,7,9-Tetramethyl-5-dezine- 4, 7-diol 0.1 part

REFERENCE EXAMPLE 6 Instead of the crude copper phthalocyanine of Reference Example 3, 280 parts of a yellow pigment ("Hanza Brilliant Yellow 9GX" manufactured by Hoechst) was used and treated in the same manner as in Reference Example 3, and the solid content was determined by the same operation. A 50% aqueous dispersion of an acrylic-treated pigment was obtained, and the following raw materials were placed in a sand mill and dispersed for 3 hours.

Yellow pigment (aqueous dispersion of acryl-treated pigment having a solid content of 50%) 55.0 parts Acrylic resin aqueous solution (“Johncryl 61J” manufactured by Johnson Polymer Co.) 7.0 parts Dispersant (Emulgen A- manufactured by Kao Corporation) 90 ") 4.0 parts Purified water 56.0 parts Diethylene glycol monobutyl ether 3.0 parts N-methyl {2} pyrrolidone 3.0 parts 2,4,7,9-Tetramethyl-5-decyne-4,7- 1.0 part of diol 1.0 part of ethylene glycol After dispersion, it was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently filtered through a 0.45 μm membrane filter to produce a recording solution. The evaluation results are shown in Tables 1 to 4.

The above dispersion 13.0 parts Dispersant (Zeneca “Solsperse 27000” 0.2 part) Acrylic resin emulsion (Nippon Polymer “W-215”) 1.0 part Diethylene glycol 22.5 parts Fungicide (“Proxel GXL” manufactured by Zeneca) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Purified water 63.53 parts 2,4,7,9-Tetramethyl-5-decyne-4,7-diol 0.1 parts

[0099]

Example 7-1 In place of the crude copper phthalocyanine of Example 3-1, 280 parts of "Lionol Blue KLH-T" (manufactured by Toyo Ink Mfg. Co., Ltd.) were used, and the solid content was changed in the same manner as in Example 3-1. A 50% aqueous dispersion of the treated pigment was obtained. The following raw materials were mixed and dispersed in a sand mill for 4 hours to prepare a concentrated recording liquid for inkjet.

Blue pigment (aqueous dispersion of treated pigment having a solid content of 50% “KLH-T”) 18.0 parts Acrylic resin aqueous solution (“Johncryl 62” manufactured by Johnson Polymer) 3.8 parts Dispersant (manufactured by Kao Corporation) "Emulgen A-90") 3.0 parts Purified water 74.5 parts Ethylene glycol 6.0 parts After dispersing, mixing with the following, mixing, filtering through a 1μ membrane filter, followed by 0.45μ The solution was filtered through a membrane filter to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 13.9 parts Dispersant (“Solsperse 27000” manufactured by Zeneca) 0.3 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd.) 2.1 parts Glycerin 24.0 parts Antifungal 0.15 parts Purified water 63.53 parts 2,4,7,9-tetramethyl-5-decine-4,7-diol 0.1 part

Comparative Example 2 The following raw materials were mixed and dispersed in a sand mill for 8 hours to prepare a concentrated recording liquid for inkjet.

Blue pigment (“KLH-T” manufactured by Toyo Ink Manufacturing Co., Ltd.) 8.0 parts Acrylic resin aqueous solution (“Johncryl 62” manufactured by Johnson Polymers) 3.8 parts Dispersant (“Solsperse 27000” manufactured by Zeneca) 4.0 parts Purified water 82.5 parts Ethylene glycol 6.0 parts After dispersing, the mixture was mixed with the following, and then filtered through a 1μ membrane filter. Was few. In addition, since filtration with a 0.45 μm membrane filter was extremely difficult, no evaluation was made on the printing state, jetting characteristics, and the like.

The above dispersion 13.9 parts Dispersant (“Solsperse 27000” manufactured by Zeneca) 0.3 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd.) 2.1 parts Glycerin 24.0 parts Antifungal 0.15 parts Purified water 63.53 parts 2,4,7,9-Tetramethyl-5-decyne-4,7-diol 0.1 part

[0104]

Example 7-2 In place of the crude copper phthalocyanine of Example 3-2, 280 parts of "Lionol Blue KLH-T" (manufactured by Toyo Ink Mfg. Co., Ltd.) were used, and the solid content was changed in the same manner as in Example 3-2. A 50% aqueous dispersion of an acrylic treated pigment was obtained.
The following ingredients are mixed and dispersed in a sand mill for 4 hours.
A concentrated recording liquid for inkjet was prepared.

Blue pigment (aqueous dispersion of acryl-treated pigment having a solid content of 50% “KLH-T”) 20.0 parts Acrylic resin aqueous solution (“Johncryl 62” manufactured by Johnson Polymer) 2.8 parts Dispersant (Zeneca) 4.0 parts Purified water 74.5 parts Ethylene glycol 6.0 parts After dispersion, the mixture was mixed with the following, mixed, filtered through a 1μ membrane filter, and then filtered with a 0.45μ membrane. The solution was filtered through a filter to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 13.5 parts Dispersant (“Solsperse 27000” manufactured by Zeneca) 0.2 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd.) 1.0 part Glycerin 25.0 parts Antifungal 0.15 parts of agent ("Sodium Omazine" manufactured by Nippon Olin)

Reference Example 7 In place of crude copper phthalocyanine of Reference Example 3, 280 parts of Lionol Blue KLH-T (manufactured by Toyo Ink Mfg. Co., Ltd.) was used. % Of an acrylic-treated pigment aqueous dispersion was obtained, and the following raw materials were placed in a sand mill and dispersed for 3 hours.

Blue pigment (aqueous dispersion of acryl-treated pigment having a solid content of 50% KLH-T) 20.0 parts Acrylic resin aqueous solution (“Johncryl 62” manufactured by Johnson Polymer) 2.8 parts Dispersant (manufactured by Zeneca) Solsperse 27000 ") 4.0 parts Purified water 74.5 parts Ethylene glycol 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently filtered through a 0.45 μm membrane filter to produce a recording solution. The evaluation results are shown in Tables 1 to 4.

The above dispersion 13.5 parts Dispersant (“Solsperse 27000” manufactured by Zeneca) 0.2 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd.) 1.0 part Glycerin 25 parts Fungicide ( "Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 parts

[0109]

Example 8 Red pigment ("Poster Palm Pink E" manufactured by Hoechst): 250 parts, pigment derivative (P- [CH ₂ NH)
((CH ₂ ) ₄ N (C ₂ H ₅ ) ₂ ] ₂ P is a quinacridone residue)
8 parts, 2500 parts of sodium chloride, and 160 parts of polyethylene glycol 300 (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, the mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and then filtered and washed with water 5 times to repeat sodium chloride and solvent. And an aqueous pigment dispersion having a solid content of 50% (treated pigment dispersion) was obtained. The following materials were placed in a paint shaker and dispersed for 4 hours to prepare a concentrated recording liquid for inkjet.

Red pigment (treated pigment dispersion, 50% product) 30.0 parts Acrylic resin aqueous solution (“Johncryl 62” solid content: 31.0%, manufactured by Johnson Polymer) 3.0 parts Dispersant (“Emulgen A-” manufactured by Kao Corporation) 90 ") 1.0 part Purified water 50.0 parts Glycerin 6.0 parts After dispersing, mixing with the following, mixing, filtration through a 1μ membrane filter, followed by filtration through a 0.45μ membrane filter Then, a recording liquid was produced. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 1 to 4.

The above dispersion 13.5 parts Dispersant (“Emulgen A-90” manufactured by Kao Corporation) 0.2 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd.) 1.0 part Diethylaminoethanol 0.1 Part Ethylene glycol 10.0 part Antifungal agent ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 part Sodium salt of ethylenediaminetetraacetylic acid 0.02 part Purified water 63.53 parts Other than "HG5130" manufactured by Epson Then, the recording liquid was put into a cartridge of “thinkjet” manufactured by Hewlett-Packard Company, and recording was performed.
Good recorded matter was obtained as in the case of G5130 ″, and the water resistance was also sufficient.

[0112]

[Comparative Example 3] The following raw materials were placed in a paint shaker.
The mixture was dispersed for a time to prepare a concentrated recording liquid for inkjet.

Red pigment ("Poster Palm Pink E" manufactured by Hoechst) 15.0 parts Acrylic resin aqueous solution ("Johncryl 62" solid content 31.0%, manufactured by Johnson Polymer) 3.0 parts Dispersant ("Emulgen" manufactured by Kao Corporation) A-90 ") 1.0 part Purified water 50.0 parts Glycerin 6.0 parts After dispersion, the mixture was mixed with the following. After mixing, filtration was performed with a 1 μm membrane filter, and the amount of filtration was significantly smaller than that in Example 8. Further, since the filtration with a 0.45 μ filter was very difficult, the printing state, the ejection characteristics, and the like were not evaluated.

The above dispersion 13.5 parts Dispersant (Emulgen A-90 manufactured by Kao Corporation) 0.2 part Acrylic resin emulsion (W-215 manufactured by Nippon Polymer Co., Ltd.) 1.0 part Diethylaminoethanol 0.1 part Ethylene glycol 10.0 parts Fungicide ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 parts Sodium salt of ethylenediaminetetraacetic acid 0.02 parts Purified water 63.53 parts

[0115]

Example 9 250 parts of crude copper phthalocyanine (copper phthalocyanine manufactured by Toyo Ink Mfg. Co., Ltd.), sodium chloride: 25
00 parts, the following blue pigment derivatives (ae): 20 parts, and polyethylene glycol 300 (manufactured by Tokyo Chemical Industry Co., Ltd.): 1
60 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, the mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and then filtered and washed with water 5 times to repeat sodium chloride and solvent. , An aqueous pigment dispersion having a solid content of 50% (pigment derivative-treated pigment dispersion) was obtained.

[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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The following materials were placed in a sand mill and dispersed for 3 hours to prepare a concentrated recording liquid for ink jet.

Blue pigment (pigment derivative-treated pigment dispersion 50% product) 30.0 parts Acrylic resin aqueous solution ("Johncryl 62" solid content: 31.0%, manufactured by Johnson Polymer) 3.0 parts Dispersant (manufactured by Kao Corporation) "Emulgen 420") 1.0 part Purified water 50.0 parts Glycerin 6.0 parts After dispersing, mixing with the following, mixing, filtering through a 1μ membrane filter, followed by a 0.45μ membrane filter And filtered to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 5 and 6.

The above dispersion 13.5 parts Dispersant (“Emulgen 420” manufactured by Kao Corporation) 0.2 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd.) 1.0 part Ethylene glycol 10.0 parts Mold agent ("Sodium Omazine" manufactured by Nippon Olin Co., Ltd.) 0.15 parts Sodium salt of ethylenediaminetetraacetylic acid 0.02 parts Purified water 63.53 parts

[0124]

Example 10: Red pigment ("Poster Palm Pink E" manufactured by Hoechst): 250 parts, the following pigment derivatives f to q: 12
Parts, sodium chloride: 2500 parts, and polyethylene glycol 300 (manufactured by Tokyo Chemical Industry Co., Ltd.): 160 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, the mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and filtered and washed with water for 5 hours.
The aqueous pigment dispersion (treated pigment dispersion) having a solid content of 50% was obtained by repeating the process to remove the sodium chloride and the solvent.

[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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The following materials were placed in a paint shaker and
The mixture was dispersed for a time to prepare a concentrated recording liquid for inkjet.

Red pigment (processed pigment dispersion 50% product) 30.0 parts Acrylic resin aqueous solution ("Joncryl 62" solid content 31.0%, manufactured by Johnson Polymer) 3.0 parts Dispersant (Kao Corporation, "Emulgen") A-90 ") 1.0 part Purified water 50.0 parts Glycerin 6.0 parts After dispersing, mixing with the following, mixing, filtering through a 1μ membrane filter, followed by a 0.45μ membrane filter. And filtered to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 7 and 8.

The above dispersion 13.5 parts Dispersant (“Emulgen 420” manufactured by Kao Corporation) 0.2 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd.) 1.0 part Ethylene glycol 10.0 parts Glycerin 10.0 parts Antifungal agent ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 part Sodium salt of ethylenediaminetetraacetylic acid 0.02 part Purified water 63.53 parts In addition to "HG5130" manufactured by Epson Corporation, The recording liquid was put into a cartridge of “thinkjet” manufactured by Hewlett-Packard Company, and recording was performed.
Good recorded matter was obtained as in the case of G5130 ″, and the water resistance was also sufficient.

[0140]

Example 11 Using 260 parts of a yellow pigment ("Hosta Palm Yellow H3G" manufactured by Hoechst), the following pigment derivatives (r to
x): 12 parts, sodium chloride: 2500 parts, polyethylene glycol 300 (manufactured by Tokyo Kasei): 160 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, the mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and then filtered and washed with water 5 times to repeat sodium chloride and solvent. And an aqueous pigment dispersion having a solid content of 50% (treated pigment dispersion) was obtained.

[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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The following raw materials were placed in a sand mill and dispersed for 4 hours to prepare a concentrated recording liquid for inkjet.

Yellow pigment (treated pigment dispersion 50% product) 30.0 parts Acrylic resin aqueous solution (Johncryl 62, manufactured by Johnson Polymer Co., 31.0% solid content) 4.0 parts Dispersant (Kao Corporation, “Emulgen”) A-90 ") 1.5 parts Purified water 50.0 parts Glycerin 6.0 parts After dispersion, the mixture was mixed with the following, mixed, filtered through a 1 μ membrane filter, and then passed through a 0.45 μ membrane filter. And filtered to produce a recording solution. Various evaluations were made in the same manner as in Example 1, and the results are shown in Tables 9 and 10.

The above dispersion 13.5 parts Dispersant (“Emulgen A-90” manufactured by Kao Corporation) 0.2 part Acrylic resin emulsion (“W-215” manufactured by Nippon Polymer Co., Ltd.) 1.0 part Ethylene glycol 10.0 Part Glycerin 10.0 part Dimethylaminoethanol 0.1 part Antifungal agent ("Sodium Omazine" manufactured by Nippon Olin Co.) 0.15 part Sodium salt of ethylenediaminetetraacetylic acid 0.02 part Purified water 63.53 parts Epson Corporation In addition to "HG5130" manufactured by Hewlett-Packard Company, this recording liquid was put into a cartridge of "thinkjet" manufactured by Hewlett-Packard Company, and recording was performed.
Good recorded matter was obtained as in the case of G5130 ″, and the water resistance was also sufficient.

[0151]

[Table 1]

[0152]

[Table 2]

[0153]

[Table 3]

[0154]

[Table 4]

Dispersion time 1 *: Salt milling treatment time Dispersion time 2 *: Dispersion time with a sand mill or paint shaker Water resistance 1 *: When a water drop is dropped on a recorded matter.・ Water resistance 2 *: When the recorded matter is immersed in water.

[0156]

[Table 5]

[0157]

[Table 6]

Dispersion time 1 *: Salt milling treatment time Dispersion time 2 *: Dispersion time with a sand mill or paint shaker Water resistance 1 *: When a water drop is dropped on a recorded matter.・ Water resistance 2 *: When the recorded matter is immersed in water.

[0159]

[Table 7]

[0160]

[Table 8]

Dispersion time 1 *: Salt milling treatment time Dispersion time 2 *: Dispersion time with a sand mill or paint shaker Water resistance 1 *: When a water drop is dropped on a recorded matter.・ Water resistance 2 *: When the recorded matter is immersed in water.

[0162]

[Table 9]

[0163]

[Table 10]

Dispersion time 1 *: Salt milling treatment time Dispersion time 2 *: Dispersion time with a sand mill or paint shaker Water resistance 1 *: When a water drop is dropped on a recorded matter.・ Water resistance 2 *: When the recorded matter is immersed in water.

When the recording solutions obtained in Examples 1 to 11 were stored at -40.degree. C. for one week and dissolved spontaneously,
When stored in a constant temperature bath for 1 month, hold at -40 ° C for 3 hours, raise the temperature to 60 ° C over 3 hours, hold at 60 ° C for 3 hours, and then 3 hours to -40 ° C After cooling and repeating this for 3 days, in each case, no precipitate was generated, the initial viscosity was maintained, and the injection characteristics were stable.

[0166]

As described above, the ink jet recording liquid of the present invention is suitable for use as an ink jet recording liquid because it has excellent water resistance and transparency while being water-soluble, and also has excellent ejection characteristics. The recording liquid for ink jet of the present invention is suitable for use in the field of recorded matter such as creation of documents in offices, marking of symbols, corrugated cardboard, numbering, and bar codes, and in the field of simple printing.

 ──────────────────────────────────────────────────の Continued on the front page (31) Priority claim number Japanese Patent Application No. Hei 7-238161 (32) Priority date September 18, 1995 (September 18, 1995) (33) Priority claim country Japan (JP) (72) Inventor Ichiro Toyoda 2-13-13 Kyobashi, Chuo-ku, Tokyo Toyo Ink Manufacturing Co., Ltd. (72) Inventor Hisashi Uraki 2-3-1-13 Kyobashi, Chuo-ku, Tokyo Toyo Ink Manufacturing Co., Ltd. (72) Inventor Jun Satake 2-3-113 Kyobashi, Chuo-ku, Tokyo Toyo Ink Manufacturing Co., Ltd. (72) Inventor Seiji Sawada 2-3-1-13 Kyobashi, Chuo-ku, Tokyo Toyo Ink Manufacturing Co., Ltd. (72) Inventor Yasuhisa Iida 2-13-13 Kyobashi, Chuo-ku, Tokyo Inside Toyo Ink Manufacturing Co., Ltd.

Claims (9)

[Claims] 1. A method for producing a water-dispersed inkjet recording liquid comprising the following steps a) to d): a) an organic pigment (A), a water-soluble inorganic salt at least 3 times by weight of the organic pigment (A); Mechanically kneading a mixture comprising at least three components of B) and a water-soluble solvent (C) to micronize the organic pigment (A); b) from the micronized mixture of the organic pigment (A) A step of removing the water-soluble inorganic salt (B) and the water-soluble solvent (C) by washing with water to obtain an aqueous dispersion of the organic pigment (A) having an average particle size of 10 to 150 nm (measured by laser scattering); c) D) a step of adding an aqueous resin to the dispersion to disperse the same; 2. The process for producing a water-dispersed inkjet recording liquid according to claim 1, wherein the mixture in step a) contains a pigment derivative (D) of the following formula (1). YZN (R ¹ ) R ² ] n (1) (where P is an organic dye residue and X is -SO _{2-
, -CO -, - CH 2 -} , - CH 2 S -, - CH 2 O
-, - O -, - COO -, - NH -, - CH 2 NHCO
At least one kind of divalent linking group selected from CH-, Y
Is a direct bond, -NR- (where R is H or carbon number 1 to
A divalent linking group selected from —O—, Z is an alkylene group having 1 to 6 carbon atoms, and R ¹ and R ² are each independently a carbon atom having 1 to 18 carbon atoms which may be substituted. Or a heterocyclic ring may be formed with R ¹ and R ² , and the heterocyclic ring may have a substituent;
Represents an integer of 1 to 3). 3. The organic pigment (A) is at least one selected from the group consisting of quinacridone organic pigments, phthalocyanine organic pigments, benzimidazolone organic pigments, isoindolinone organic pigments, and azo organic pigments. The method for producing a water-dispersed inkjet recording liquid according to claim 1, wherein: 4. The process for producing a water-dispersed inkjet recording liquid according to claim 1, wherein the dispersion in step c) comprises kneading the aqueous dispersion and the aqueous resin. 5. The method for producing an ink jet recording liquid according to claim 1, wherein the dispersion in the step c) comprises dispersing the organic pigment and the aqueous resin at an organic pigment concentration of 10 to 40% by weight. 6. The additive of step d) is selected from the group consisting of a neutralizing agent for aqueous resin, a dispersant, an aqueous solvent for maintaining wettability, a fungicide, a penetration modifier, a chelating agent and an antifoaming agent. The method for producing a water-dispersed inkjet recording liquid according to claim 1, which comprises at least one selected from the group consisting of: 7. The organic pigment (A) is contained in an amount of 0.1 to 10% by weight.
2. The method for producing a water-dispersed inkjet recording liquid according to claim 1, wherein the content is within the range of. 8. The method for producing a water-dispersed inkjet recording liquid according to claim 1, wherein the viscosity of the aqueous-dispersed inkjet recording liquid is in the range of 0.8 to 15 centipoise (25 ° C.). 9. The water-dispersed inkjet recording liquid according to claim 1, wherein the aqueous resin is mixed in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the recording liquid.