JP3024487B2 - Water-dispersible recording liquid for inkjet and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, as an ink jet recording liquid, a solution obtained by dissolving a water-soluble dye such as an acid dye, a direct dye, or a basic dye in a glycol solvent and water is widely used (Japanese Patent Application Laid-Open No. 53-53). No. 6112, JP-A-54-89811,
JP-A-55-65269). 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 spilling water easily causes dye bleeding of a recorded portion.

In order to improve such poor water resistance,
Attempts have been made to change the structure of the dye or to prepare a recording solution having a strong basicity (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 (JP-A-50-49004, JP-A-57-36692, JP-A-59-36692). -20696, JP-A-59-146889). These methods have a remarkable effect on certain types of recording paper. However, since various recording papers are used in ink jet recording, sufficient water resistance of the recorded material can be obtained with a recording liquid using a water-soluble dye. Is often not obtained.

As recording liquids having good water resistance, there are those in which an oil-soluble dye is dispersed or dissolved in a high boiling point solvent, and those in which an oil-soluble dye is dissolved in a volatile solvent. Environmentally disliked the emission of
Depending on the case where a large amount of data is recorded or where the apparatus is installed, the necessity of solvent recovery may be a problem. Therefore, in order to improve the water resistance of the recorded matter, a recording liquid in which a pigment is dispersed in an aqueous medium has been developed. However, in order to obtain the dispersion stability of the pigment, it is necessary to sufficiently reduce the size of the pigment, and in this production, it is necessary to select a compound capable of stably dispersing the pigment.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a water-dispersible recording liquid for ink jet which can obtain a recorded matter having good water resistance on any paper, and a method for easily producing the same.

[0006]

That is, the present invention provides a face
Is mixed with a compound represented by the general formula (I) and an aqueous resin.
Dispersed in water and represented by the above-mentioned pigment and the above-mentioned general formula (1).
(1) producing a concentrated aqueous dispersion having a solid content of 15% by weight or more of the compound to be obtained, and the step (1).
Water is added to the aqueous dispersion to form the pigment and the compound represented by the general formula (1).
Dispersion solids of the compounds were diluted to 8 wt% or less
Step (2) of preparing a liquid, and the amount obtained in step (2).
Filtering the dispersion liquid in the pore size of 0.65μm or less of the filter
Step (3), having a viscosity of 0.8 to 2.6 centipoise
The present invention relates to a method for producing a water-dispersible recording liquid for ink-jet recording , characterized in that

Embedded image (In the formula, n represents an integer of 3 to 10. )

The compound represented by the general formula (I) has a function of dispersing the pigment in a good manner and improving the dispersion stability of the pigment over time. It is preferable to be included in the range. When the content of the compound represented by the general formula (I) is less than 0.1% by weight,
Does not show sufficient pigment dispersing effect. If the content exceeds 10% by weight, the viscosity of the recording liquid becomes high, which may cause problems such as slow drying on the paper when printing. The compound represented by the general formula (I) is a compound represented by the general formula (II) or a compound represented by the general formula (III) singly or in a mixture. The compound represented by the general formula (II): The ratio of the compound represented by III) is from 30 to 50:10.
It is preferably 3.

[0008]

Embedded image

The water-dispersible recording liquid for ink-jet recording of the present invention contains a pigment and water in addition to the compound represented by the general formula (I), and if necessary, a coloring agent such as a dye, an aqueous solvent, an aqueous resin, a penetrant. , An antifungal agent, a chelating agent, a pH adjuster, an antifoaming agent, a neutralizing agent for an aqueous resin, and the like.

As the pigment, various pigments used for printing inks and paints can be used. Such pigments include CI yellow pigments 20, 24, 86, 93, 10
9, 110, 117, 125, 137, 138, 14
7, 148, 153, 154, 166, 168, CI Oren pigment 36, 43, 51, 55, 59, 61, CI
Red pigments 9, 97, 122, 123, 149, 168,
177, 180, 192, 215, 216, 217, 2
20, 223, 224, 226, 227, 228, 24
0, CI violet pigments 19, 23, 29, 30, 3
7, 40, 50, CI blue pigment 15, 15: 1, 15:
4, 15: 6, 22, 60, 64, CI green pigments 7, 3
6, CI brown pigments 23, 25, 26, CI black pigment 7, titanium black, and the like (illustrated by color index (CI) numbers).

The pigment may be used in the form of an aqueous slurry after the pigment is formed, or the slurry may be powdered by drying such as spray drying. However, in the production of a recording liquid, a pigment having a smaller particle diameter is preferable because the smaller the particle diameter of the pigment, the better the flying stability as the recording liquid. Alternatively, it is preferable to select a pigment that can be miniaturized in the dispersion step. The preferred particle size of the pigment is 0.2 μm or less, more preferably 0.1 μm or less, as the average particle size by centrifugal sedimentation. With such a particle diameter, the filtration operation in the production of the recording liquid is easy, and the sedimentation of the recording liquid over time is reduced. Further, a surface-treated pigment obtained by adding a functional group to the surface of the pigment may be used.

A dye may be used in the recording liquid of the present invention in such a manner that there is no problem in water fastness and light fastness for the purpose of adjusting hue, imparting density, and the like. However, the use of the dye may deteriorate the dispersion stability of the pigment, so the amount of the pigment used must be limited to 40% by weight or less, preferably 25% by weight or less of the pigment. As the dye, an acid dye, a basic dye, a direct dye, a reactive dye, a disperse dye, a metal-containing dye and the like are used. The dye is preferably a purified dye from which inorganic salts have been removed.

As the dye, CI Direct Black 1
7, 19, 32, 51, 71, 108, 146, 15
4,166, CI Acid Black 2,7,24,2
6, 31, 52, 63, 112, 118, CI Basic Black 2, CI Direct Blue 6, 22, 25,
71,90,106, CI Acid Blue 9,22,4
0, 59, 93, 102, 104, 113, 117, 1
20, 167, 229, 234, CI Basic Blue 1, 3, 5, 7, 9, 24, 25, 26, 28, 29,
CI Direct Red 1,4,17,28,83, CI
Acid Red 1,6,32,37,51,52,8
0, 85, 87, 92, 94, 115, 180, 25
6,315,317, CI Basic Red 1, 2,
9, 12, 13, 14, 37, CI Direct Yellow 1
2,24,26,98, CI Acid Yellow 11,1
7, 23, 25, 29, 42, 61, 71, CI Basic Yellow 11, 28. CI Direct Orange 34,
39, 44, 46, 60, CI Direct Violet 47, 48, CI Direct Brown 109, CI Direct Green 59, CI Acid Orange 7, 19,
CI Acid Violet 49, CI Basic Violet 7, 14, 27 and the like can be exemplified.

The aqueous solvent prevents drying of the recording liquid at the nozzle portion and solidification of the recording liquid, thereby preventing stable ejection of the recording liquid and drying of the nozzle over time. Examples of such aqueous solvents include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone,
Examples thereof include 2,4,6-hexanetriol, tetrafurfuryl alcohol, and 4-methoxy-4-methylpentanone. Further, alcohols such as methanol, ethanol and isopropyl alcohol can be used for the purpose of speeding up the drying of the recording liquid on paper. The aqueous solvent is used alone or as a mixture in the range of 2 to 50% by weight of the recording liquid. As the water as the medium of the recording liquid, ion-exchanged water or distilled water from which metal ions and the like have been removed is used.

The aqueous resin can be used to improve the dispersion stability of the pigment and the good fixation of the recording liquid to the printing medium. As the aqueous resin, a water-soluble resin soluble in water and a water-dispersible resin can be used alone or as a mixture. Such resins include acrylic resins,
Water-soluble resins such as styrene-acrylic, polyester-based, polyamide-based, and polyurethane-based resins that dissolve in water and resins that are dispersible in water are used. The recording liquid of the present invention contains ammonia, amine,
A neutralizing agent such as an inorganic alkali can be appropriately adjusted and added.

When the printing medium of the recording liquid is a permeable material such as paper, a penetrant can be added in order to stop the penetration of the recording liquid into the paper and to speed up the apparent dryness. Examples of such penetrants include glycol ethers such as diethylene glycol monobutyl ether described as aqueous solvents, alkylene glycols, polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, sodium dioctylsulfosuccinate and the like. Can be used. These have a sufficient effect when used in an amount of 5% by weight or less of the recording liquid. If the amount is more than 5% by weight, bleeding of printing and paper loss (print through) occur, which is not preferable.

The antifungal agent is used to prevent the occurrence of fungi in the recording liquid, and includes sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2, -Benzisothiazolin-3-one, 1-benzisothiazoline-
An amine salt of 3-one or the like is used. These use about 0.05 to 1.0% by weight of the recording liquid.

The chelating agent blocks metal ions in the recording liquid and prevents the deposition of metal at the nozzle portion and the deposition of insoluble substances in the recording liquid, and the like. Ethylenediaminetetraacetic acid, ethylenediamine For example, a sodium salt of tetraacetylic acid, a diammonium salt of ethylenediaminetetraacetic acid, a tetraammonium salt of ethylenediaminetetraacetic acid, and the like are used. These are 0.005 to 0.
Used in the range of 5% by weight.

Further, in order to adjust the pH of the recording liquid and obtain stability of the recording liquid or stability with the recording liquid piping in the recording apparatus, an adjusting agent such as an amine, an inorganic salt or ammonia, and a buffer such as phosphoric acid. Can be used. In addition, the circulation of the recording liquid,
An antifoaming agent may be added to prevent migration or foaming during the production of the recording liquid.

In order to further improve the dispersion of the pigment, the compound represented by the general formula (I) is added with an anionic, nonionic,
A surfactant such as a cationic or amphoteric surfactant can be added for use. 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.

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

As other additives, urea, dimethyl urea and the like can be added. For the production of recording liquid,
The pigment is mixed with the compound represented by the general formula (I), water, and, if necessary, an aqueous resin and an aqueous solvent, and dispersed with a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, or the like to obtain a solid content of 15%. Producing a concentrated dispersion of not less than% by weight. Alternatively, the pigment and the general formula (I)
Is kneaded in advance in a kneader or a two-roll mill, and further dispersed in a sand mill or the like to produce a concentrated dispersion having a solid content of 15% by weight or more. Thereafter, the recording liquid is manufactured by appropriately diluting the solid content to 8% by weight or less with water and mixing other additives. 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.

If the concentrated dispersion liquid is filtered before dilution to remove coarse particles in advance, filtration after dilution becomes easy. Filtration after dilution is sufficiently performed with a filter having a pore size of 0.65 μm or less. Furthermore, it is preferable to filter with a filter of 0.45 μ or less. Prior to the filtration by filtration, filtration by centrifugation can also be performed, thereby reducing clogging in the filtration and facilitating filter replacement. The viscosity of the recording liquid is adjusted to 0.8 to 15 cps (25 ° C.), depending on the type of the recording apparatus.
The surface tension is 25-60 dyn / cm. pH is
Although not particularly limited, it is in the range of 4 to 12, and a weak alkalinity of 7 to 9 is preferred.

The recording liquid produced according to the present invention is water-based and has extremely good water resistance, so that it is preferably used as an ink-jet recording liquid. It can be used in fields such as marking, numbering, and bar codes. Further, the light resistance is better than that of a recording liquid produced by using a dye, and a color image having excellent storage stability of a recorded matter can be formed.

[0025]

The present invention will be described below in further detail with reference to examples. In the examples, parts and% represent parts by weight and% by weight, respectively. [Example 1] Carbon black ("MA-7" manufactured by Mitsubishi Kasei Co., Ltd.) 15 parts Acrylic resin dispersion 1.3 parts ("Torkuril F-157" manufactured by Nippon Polymer Industries, NV = 40%) General formula (II) ) And a compound represented by the general formula (III) (the weight ratio of (II) to (III) is 4: 1, the average of n is 6) 3.8 parts Purified water 74 parts Glycerin 5. 8 parts Dimethylethanolamine 0.1 part The above raw materials were mixed, dispersed in a sand mill for 1 hour, and then mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording solution. Recording liquid viscosity (2
5 ° C.) was 1.8 cps. 25 parts of the above-mentioned dispersion A mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 4: 1, n is 6 on average) 2 parts Glycerin 10 parts Antifungal agent ("Sodium Omazine" manufactured by Orin Chemical Co., Ltd.) 0.15 parts Sodium salt of ethylenediaminetetraacetic acid 0.02 parts Diethylene glycol monobutyl ether 0.5 parts Silicone emulsion type water-based defoamer 0.8 parts (Anti-Home E20 manufactured by Kao Corporation) 63.53 parts of purified water This ink was recorded on plain paper using an inkjet printer (“ThinkJet” manufactured by Hewlett-Packard Company), and a good recorded matter was obtained. . We dripped water on the recording surface and examined the ink bleeding.
There was no run-off, and it had sufficient water resistance.

Example 2 15 parts of a blue pigment ("Lionol Blue 7351" manufactured by Toyo Ink Mfg. Co., Ltd.) 1.5 parts of an aqueous acrylic resin solution ("PDX6101" manufactured by Johnson Polymer, NV = 27.5%) General formula A mixture of the compound represented by formula (II) and the compound represented by formula (III) (weight ratio of (II) to (III) is 5: 1, average of n is 6) 3.0 parts Purified water 74.5 Part glycerin 6.0 parts The above-mentioned raw materials were mixed, dispersed by a sand mill for 1 hour, and then mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording solution. Recording liquid viscosity (2
5 ° C.) was 2.0 cps. 13.5 parts of the above dispersion A mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 5: 1, and the average of n is 6) 0.2 parts Acrylic resin dispersion 1.0 part (Nippon Polymer Kogyo Co., Ltd. "Torkuril W-251", NV = 45%) Ethylene glycol 10 parts Preservative (Olin Chemical Co., Ltd. "Sodium Omazine") 0.15 parts Ethylenediamine Tetraacetylic acid 0.02 parts Purified water 63.53 parts 2-Ethylhexanol 0.1 parts 2,4,7,9-Tetramethyl-5-decyne-4,7-diol 0.1 parts This ink Was recorded on plain paper using an inkjet printer (“HG5130” manufactured by Seiko Epson Corporation), and a good recorded matter was obtained. Water was dripped on the recording surface to examine the bleeding of the ink. As a result, there was no bleeding of the ink and no bleeding out, indicating that the ink had sufficient water resistance.

[Example 3] 20 parts of a yellow pigment ("Lionol Yellow 22-2845" manufactured by Toyo Ink Mfg. Co., Ltd.) 2.8 parts of an aqueous acrylic resin solution ("PDX6101" manufactured by Johnson Polymer, NV = 27.5%) Nonionic surfactant ("Emulgen 420" manufactured by Kao Corporation) 2.1 parts Mixture of compound represented by general formula (II) and compound represented by general formula (III) (weight of (II) and (III)) The ratio was 10: 1, and the average of n was 5) 4.0 parts Purified water 74.5 parts Glycerin 6.0 parts The above-mentioned raw materials were mixed, dispersed by a sand mill for 1 hour, and then mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording solution. Recording liquid viscosity (2
5 ° C.) was 2.2 cps. 13.5 parts of the above-mentioned dispersion A mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 10: 1, and the average of n is 5) 0.2 parts Acrylic resin dispersion 2.0 parts (Torkuril W-251, manufactured by Nippon Polymer Industries, NV = 45%) Diethylene glycol 10 parts Preservatives ("Sodium Omazine", manufactured by Ohrin Chemical Co.) 0.15 parts Ethylenediaminetetra Acetic acid 0.02 parts Purified water 63.53 parts 2-ethylhexanol 0.1 parts 2,4,7,9-Tetramethyl-5-decyne-4,7-diol 0.1 parts When recording was performed on plain paper using “HG5130” manufactured by Seiko Epson Corporation, a good recorded matter was obtained. Water was dripped on the recording surface to examine the bleeding of the ink. As a result, there was no bleeding of the ink and no bleeding out, indicating that the ink had sufficient water resistance.

Example 4 22 parts of a red pigment ("Hosta Palm Pink E-02" manufactured by Hoechst) Acrylic resin aqueous solution 7 parts ("Johncryl 61J" manufactured by Johnson Polymer, NV = 30.5%) General formula Compound represented by (II) (average of n is 7) 4.0 parts Purified water 59 parts Diethylene glycol monobutyl ether 3 parts N-methyl-2-pyrrolidone 3 parts 2,4,7,9-tetramethyl-5-decyne -4,7-diol 1 part Ethylene glycol 1 part The above-mentioned raw materials were mixed, dispersed for 1 hour by a sand mill, and then 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. Recording liquid viscosity (2
5 ° C.) was 2.6 cps. 13.5 parts of the above dispersion A mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 10: 1, and the average of n is 6) 0.2 parts Acrylic resin dispersion 2.0 parts (Torkuril W-251, manufactured by Nippon Polymer Industries, NV = 45%) 15 parts of diethylene glycol Antifungal agent ("Sodium Omazine", manufactured by Ohrin Chemical Company) 0.15 parts Ethylenediamine Tetraacetylic acid 0.02 parts Purified water 63.53 parts 2-ethylhexanol 0.1 parts 2,4,7,9-Tetramethyl-5-decyne-4,7-diol 0.1 parts When recording was performed on plain paper using a printer ("HG5130" manufactured by Seiko Epson Corporation), a good recorded matter was obtained. Water was dripped on the recording surface to examine the bleeding of the ink. As a result, there was no bleeding of the ink and no bleeding out, indicating that the ink had sufficient water resistance.

[Example 5] 25 parts of yellow pigment ("Hansa Brilliant Yellow 9GX" manufactured by Hoechst) Acrylic resin aqueous solution 7 parts ("Johncryl 61J" manufactured by Johnson Polymer, NV = 30.5%) A mixture of the compound represented by II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 10: 1, the average of n is 6) 4.0 parts Purified water 56 parts Diethylene glycol mono Butyl ether 3 parts N-methyl-2-pyrrolidone 3 parts 2,4,7,9-Tetramethyl-5-decyne-4,7-diol 1 part Ethylene glycol 1 part After time dispersion, it was mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording solution. Recording liquid viscosity (2
5 ° C.) was 2.3 cps. 13.0 parts of the above-mentioned dispersion mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 10: 1, and the average of n is 6) 0.2 parts Acrylic resin dispersion 2.0 parts (Tokuril W-251 manufactured by Nippon Polymer Industries, NV = 45%) Diethylene glycol 10.5 parts Antifungal agent (Proxel GXL manufactured by Zeneca) 0.15 Part Ethylenediaminetetraacetylic acid 0.02 part Purified water 63.53 parts 2-ethylhexanol 0.1 part 2,4,7,9-tetramethyl-5-decyne-4,7-diol 0.1 part This ink Was recorded on plain paper using an inkjet printer (“HG5130” manufactured by Seiko Epson Corporation), and a good recorded matter was obtained. Water was dripped on the recording surface to examine the bleeding of the ink. As a result, there was no bleeding of the ink and no bleeding out, indicating that the ink had sufficient water resistance.

Example 6 20 parts of a blue pigment ("Lionol Blue KLH-T" manufactured by Toyo Ink Manufacturing Co., Ltd.) 2.8 parts of an aqueous acrylic resin solution ("PDX6101" manufactured by Johnson Polymer, NV = 30.5%) A mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 10: 1, the average of n is 6) 4.0 parts purified water 74 5.5 parts Ethylene glycol 6.0 parts The above raw materials were mixed, dispersed by a sand mill for 1 hour, and then mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording solution. Recording liquid viscosity (2
5 ° C.) was 2.5 cps. 13.5 parts of the above dispersion A mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 10: 1, and the average of n is 6) 0.2 parts Polyester resin aqueous solution 4.0 parts (Toyobo Co., Ltd. "Vylonal MD-1400", NV = 30%) Diethylene glycol 10 parts Antifungal agent (Olin Chemical Co., Ltd. "Sodium Omazine") 0.15 parts Ethylenediaminetetraacetic Acid 0.02 parts Purified water 63.53 parts 2-ethylhexanol 0.1 parts 2,4,7,9-Tetramethyl-5-decyne-4,7-diol 0.1 parts This ink is an ink jet printer. When recording was performed on plain paper using “HG5130” manufactured by Seiko Epson Corporation, a good recorded matter was obtained. Water was dripped on the recording surface to examine the bleeding of the ink. As a result, there was no bleeding of the ink and no bleeding out, indicating that the ink had sufficient water resistance.

Example 7 15 parts of carbon black ("Special Black 4A" manufactured by Degussa) 1.3 parts of an acrylic resin dispersion ("Torkuril F-157" manufactured by Nippon Polymer Industries, NV = 40%) General formula A mixture of the compound represented by formula (II) and the compound represented by formula (III) (weight ratio of (II) to (III) is 10: 1, average of n is 6) 3.5 parts Purified water 74 parts Glycerin 5.8 parts Dimethylethanolamine 0.1 part The above-mentioned raw materials were mixed, dispersed in a sand mill for 1 hour, and then mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording solution. Recording liquid viscosity (2
5 ° C.) was 2.2 cps. 25 parts of the above-mentioned dispersion, a mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 10: 1, and the average of n is 6) 2 parts Glycerin 10 parts Preservatives ("Sodium Omazine" manufactured by Ohlin Chemical Co., Ltd.) 0.15 parts Sodium salt of ethylenediaminetetraacetic acid 0.02 parts Diethylene glycol monobutyl ether 0.5 parts Antifoaming agent ("Surfinol 104E manufactured by Air Products") )) 0.3 parts Purified water 63.53 parts When this ink was recorded on plain paper using an ink jet printer ("ThinkJet" manufactured by Hewlett-Packard Co.), a good recorded matter was obtained. We dripped water on the recording surface and examined the ink bleeding.
There was no run-off, and it had sufficient water resistance.

Example 8 Red pigment ("Hosta Palm Pink E-02" manufactured by Hoechst) 22 parts Red dye ("Fisco Pink 353" manufactured by Orient Chemical Industries) 2.0 parts Acrylic resin aqueous solution 7 parts (Johnson Polymer) "Joncryl 61J", NV = 30.5%) Compound represented by formula (II) (average of n is 6) 4.0 parts Purified water 59 parts Diethylene glycol monobutyl ether 3 parts N-methyl-2- Pyrrolidone 3 parts 2,4,7,9-Tetramethyl-5-decyne-4,7-diopole 1 part Glycerin 1 part The above raw materials were mixed, dispersed for 1 hour by a sand mill, and then 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. Recording liquid viscosity (2
5 ° C.) was 2.5 cps. 13.5 parts of the above dispersion A mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 10: 1, and the average of n is 6) 0.2 parts Acrylic resin dispersion 1.0 part ("Tokuril W-251" manufactured by Nippon Polymer Industries, NV = 45%) Glycerin 10 parts Fungicide ("Sodium Omazine" manufactured by Ohrin Chemical Co.) 0.15 parts Ethylenediamine Tetraacetic acid sodium salt 0.02 parts Purified water 63.53 parts 2-ethylhexanol 0.1 parts 2,4,7,9-Tetramethyl-5-decyne-4,7-diol 0.1 parts This ink Was recorded on plain paper using an inkjet printer (“HG5130” manufactured by Seiko Epson Corporation), and a good recorded matter was obtained. Water was dripped on the recording surface to check the bleeding of the ink. As a result, the ink did not flow out and had sufficient water resistance.

Example 9 Red pigment ("Hosta Palm Pink E" manufactured by Hoechst) 22 parts Red dye ("Edible Red 105" manufactured by Eizen) 3 parts Acrylic resin aqueous solution 4 parts ("PDX6101" manufactured by Johnson Polymer) , NV = 30.5%) A mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 10: 1, and the average of n is 6) 5 parts) Purified water 60 parts Glycerin 6 parts The above raw materials were mixed, dispersed by a sand mill for 1 hour, and then mixed with the following. After mixing, the mixture was filtered through a 1 μm membrane filter and subsequently through a 0.45 μm membrane filter to produce a recording solution. Recording liquid viscosity (2
5 ° C.) was 2.5 cps. 13.0 parts of the above-mentioned dispersion mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III) (the weight ratio of (II) to (III) is 10: 1, and the average of n is 6) 0.4 parts Acrylic resin dispersion 2.0 parts (Torkuril W-251, manufactured by Nippon Polymer Industries, NV = 45%) Glycerin 10 parts Fungicide (Proxel GXL, manufactured by Zeneca) 0.15 parts Ethylenediamine Tetraacetylic acid sodium salt 0.03 part Purified water 64 parts Isopropyl alcohol 2 parts This ink was recorded on plain paper using an inkjet printer ("HG5130" manufactured by Seiko Epson Corporation), and a good recorded matter was obtained. Was done.

An aqueous sodium hydroxide solution was added to the ink-jet inks obtained in Examples 1 and 7 to adjust the conductivity to 0.8.
Adjusted to mS or more. This ink can print stably from the 35μ nozzle of a continuous jet (sweet) ink jet printer, and the recorded characters have good water resistance without running out or bleeding even if water is dripped. showed that. In addition, the ink jet inks obtained in Examples 1 to 8 can perform stable printing from the 40 μ nozzles of an on-demand type ink jet printer, and the recorded characters may flow out or bleed even if water is dripped. And good water resistance was exhibited.

The inks obtained in Examples 1 to 9 were heated at -40 ° C.
After storage for 1 week at, it was naturally thawed, but the initial viscosity was maintained and stable injection characteristics were exhibited. Further, it was stored in a constant temperature bath at 60 ° C. for one month, but the initial viscosity was maintained and stable injection characteristics were exhibited. The ink was cycled for 3 days (holding for 3 hours) while giving a temperature change from -40 ° C to 60 ° C, and all inks did not generate precipitates and maintained a good initial state. Was. Therefore, good printing and stable ejection characteristics were exhibited.

[0036]

According to the present invention, it is possible to obtain an ink jet recording liquid which gives a recorded matter having good water resistance while using water as a medium. As a result, the restrictions on the recording medium are greatly reduced, and it is expected that the use of the aqueous recording liquid, which has often been short of water resistance due to the influence of the recording medium, can be expected.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yasuhisa Iida 2-3-1 Kyobashi, Chuo-ku, Tokyo Examiner, Naoko Matsumoto, Toyo Ink Manufacturing Co., Ltd. (56) References JP-A-6-122835 (JP, A) JP-A-3-185075 (JP, A) JP-A-56-58078 (JP, A) JP-A-56-147859 (JP, A) JP-A-3-162466 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) C09D 11/00 C09B 67/20 C09D 17/00 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A pigment or a compound represented by the general formula (I)
And the above-mentioned pigment and
And step (1) the solid content of the compound to produce an aqueous dispersion of a concentrated form of above 15% by weight represented by the general formula (1), said step
Water is added to the aqueous dispersion obtained in (1), and
The solid content of the compound represented by the general formula (1) is 8% by weight or less.
(2) preparing a diluted dispersion of
And ( 3) filtering the dispersion obtained in (2) with a filter having a pore size of 0.65 μm or less .
A method for producing a water-dispersible recording liquid for inkjet, which has a temperature of 8 to 2.6 centipoise (25 ° C.) . Embedded image (In the formula, n represents an integer of 3 to 10.) 2. A compound represented by the general formula (1):
The method for producing a water-dispersible recording liquid for inkjet according to claim 1, wherein the amount of the liquid is 10 to 10% by weight . 3. The aqueous dispersion type for ink jet according to claim 1, wherein the compound represented by the general formula (I) is a mixture of the compound represented by the general formula (II) and the compound represented by the general formula (III). Manufacturing method of recording liquid. Embedded image (In the formula, n represents an integer of 3 to 10.) 4. A claim that contains a neutralizing agent in the aqueous resin to claim 1
4. The method for producing a water-dispersible recording liquid for inkjet according to any one of items 3 to 3 .