JP3175516B2 - Ink jet recording liquid and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for dispersing a pigment,
The present invention relates to an ink jet recording liquid having excellent water resistance and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as an ink jet recording liquid, a liquid obtained by dissolving a water-soluble dye such as an acid dye, a direct dye or a basic dye in a glycol-based solvent and water has been widely used (for example, see Japanese Patent Application Laid-Open No. 53─61412, JP 54 特 開
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 of water easily causes dye bleeding of a recorded portion.

In order to improve such poor water resistance,
Attempts have been made to change the structure of the dye or to prepare a recording solution having a strong basicity (for example, see JP-A-56-5786).
2 etc.). Further, it is also attempted to improve the water resistance by making good use of the reaction between the recording paper and the recording liquid (for example, Japanese Patent Application Laid-Open Nos. 50-49004, 57-36692, and 59-20696). And 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, a recording solution using a water-soluble dye has sufficient water resistance. Is often not obtained.

[0004] Examples of recording liquids having good water resistance include those in which an oil-soluble dye is dispersed or dissolved in a high boiling point solvent and those in which an oil-soluble dye is dissolved in a volatile solvent. Environmentally disliked the emission of
Depending on the case where a large amount of recording is performed or where the apparatus is installed, the necessity of solvent recovery or the like may become a problem. Therefore, in order to improve the water resistance of the recorded matter, a recording liquid in which a pigment is dispersed in an aqueous medium has been developed. However, in 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 ink jet recording liquid capable of obtaining a recorded matter having good water resistance on any paper and an easy method for producing the same.

That is, the present invention relates to an ink jet recording
Based on the total composition of the liquid, the pigment from 0.5 to 10% by weight, 0.1 to 10% by weight aqueous resin, surfactant 0.1-10 fold
Pigment represented by an amount% and the general formula (1) Dispersant 0.00
The present invention relates to an ink jet recording liquid containing 1 to 5% by weight . General formula (1) P- [XYZN (R ¹ ) R ² ] n (where P is an organic dye residue or a heterocyclic residue , X
It is _{-SO 2 -, - CO -,} - CH 2 -, - O -, - CO
A divalent linking group selected from O-, -NH- or a combination thereof, Y is a direct bond or -N (R)-(where R is H or an alkyl group having 1 to 18 carbon atoms or ZN ( R
¹ ) R ² ) or —O— or Z is an alkylene group having 1 to 6 carbon atoms, R ¹ and R ² are each independently an optionally substituted alkyl group having 1 to 18 carbon atoms or R ¹ and R ^{And 2 represent an} optionally substituted heterocyclic ring which may contain N, O or S, and n represents an integer of 1 to 3, respectively. )

As the pigment of the present invention, various organic pigments and inorganic pigments used for printing inks and paints can be used. For example, as organic pigments, phthalocyanine pigments, insoluble azo pigments, azo lake pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perinones Pigments, perylene pigments, isoindolinone pigments, thioindigo pigments, and as inorganic pigments, carbon black, iron oxide, lead white, lead red, ultramarine, navy blue, cobalt oxide, titanium dioxide, titanium dioxide-coated mica, Strontium chromate, titanium yellow, titanium black, zinc chromate, iron black, molybdenum red, molybdenum white, lithopone, emerald green, cadmium yellow, cadmium red, cobalt blue, etc. Can.

[0008] Such a pigment may be used in the form of an aqueous slurry or a wet cake after the formation of the pigment.
This 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 flight stability as the recording liquid. Alternatively, it is preferable to select a pigment that can be miniaturized in the dispersion step. The preferred pigment particle size is
The average particle size by the centrifugal sedimentation method is 0.2 μm or less, and more preferably 0.1 μm or less. With such a particle size, the filtration operation in the production of the recording liquid is easy, and the sedimentation in storage of the recording liquid is reduced. The amount of the pigment is 0.5 to 10% by weight, preferably 2 to 4% by weight, based on the total composition of the ink jet recording liquid.

In the present invention, the pigment dispersant of the general formula (1) is
Pigment dispersion of a recording liquid is further refined and stabilized, and ejection stability from nozzles and storage stability are improved. General formula (1)
Examples of the organic dye constituting the organic dye residue represented by P include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyrimidine, anthanthrone, There are indanthrone type, flavanthrone type, perinone type, perylene type, thioindigo type and the like. These dyes can be arbitrarily selected, but those having a hue close to the pigment used are industrially more advantageous. As the heterocyclic ring constituting the heterocyclic residue include thiophene, furan, and xanthene, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, indole, quinoline, carbazole, acridine, is Akurido down like . When P is a heterocyclic ring, the pigment dispersant of the general formula (1) can be obtained that is hardly colored.

X is -SO _2- , -CO-, -CH
_{2 -, - O -, -} COO -, - an NH- or a combination thereof, preferably _{-SO 2 -, - CO -,} - C
H ₂ —, —CH ₂ NHCOCH ₂ — and the like. R ¹ , R
^{When 2} is an alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group is preferable. These alkyl groups may be branched or substituted up to a maximum of 18 carbon atoms. In some cases, R ¹ and R ² may be linked to each other to further contain N, O or S.
A 6-membered or 6-membered heterocyclic ring may be formed. The amount of the pigment dispersant is preferably 0.001 to 5% by weight based on the total composition of the ink jet recording liquid.

The pigment dispersant of the present invention may be used in the form of a dry powder when the pigment is dispersed, or may be used by mixing with the pigment in advance. Solvent or mineral acid, when using those dissolved or dispersed in organic acid aqueous solution, added to the pigment water or solvent slurry and adsorbed on the surface of the pigment, or for azo pigments during coupling, phthalocyanine pigment, For quinacridone pigments and dioxazine pigments, a method of adding a powder or solution or dispersion of a pigment dispersant during a pigmentation step such as a salt milling method and a sulfuric acid dissolving method, adsorbing the pigment on the surface of the pigment, filtering and drying as necessary. May be used as a pigment composition obtained by the above method.

In the present invention, the aqueous resin can be used to improve the dispersion stability of the pigment and the 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. Examples of such a resin include water-soluble resins such as acrylic copolymers, polyesters, polyamides, and polyurethanes that are soluble in water and resins that are dispersible in water. These resins are
If necessary, a neutralizing agent such as ammonium, amine or inorganic alkali can be appropriately adjusted and added.

The acrylic copolymer resin is composed of 50 to 80% by weight of an alkyl (meth) acrylate, acrylic acid,
5 to 30% by weight of a carboxylic acid-containing monomer such as methacrylic acid, maleic acid and itaconic acid and 0 to 2 of other monomers
It is a resin having a weight average molecular weight of 5,000 to 300,000 and an acid value of 1 to 200, obtained by emulsion polymerization or solution polymerization of 0% by weight in a water-soluble solvent. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate. ) Isobutyl acrylate,
There are 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate and the like. Examples of the other monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, acrylamide, N-methylolacrylamide, diacetone acrylamide, glycidyl (meth) acrylate, styrene, vinyltoluene, and acetic acid. Examples include vinyl, acrylonitrile, vinyl alcohol, and ethylene. The aqueous resin is 0.1 to 10% by weight, preferably 0.1 to 10% by weight, based on the total composition of the ink jet recording liquid.
5 to 3% by weight is blended.

In the present invention, anionic, nonionic, cationic and amphoteric surfactants can be used as the surfactant. 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. Examples thereof include oxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, and polyoxyethylene glycerol fatty acid ester. Nonionic activators 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, glycerin fatty acid ester , Polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine-based, silicone-based nonionic activators. Examples of the cationic activator include an alkylamine salt, a quaternary ammonium salt, an alkylpyridinium salt, and an alkylimidazolium salt. Examples of the zwitterionic activator include alkyl betaine, alkylamine oxide, phosphadylcholine and the like. The surfactant is 0.1 to 0.1 based on the total composition of the ink jet recording liquid.
10% by weight, preferably 0.5 to 3% by weight is blended.

The recording liquid of the present invention may contain an aqueous solvent, a penetrant, a preservative and the like in addition to pigment, water, a pigment dispersant, an aqueous resin, and a surfactant. , A chelating agent, a pH adjuster, an antifoaming agent, and the like. The dye can be used in such a form that there is no problem in water resistance and light resistance for the purpose of adjusting the hue of the pigment, giving the concentration, and the like. 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. Examples of the dye include an acid dye, a basic dye, a direct dye, a reactive dye, a disperse dye, and a metal-containing dye. These dyes are preferably purified dyes from which inorganic salts have been removed.

The aqueous solvent is for preventing the recording liquid from drying at the nozzle portion and solidifying the recording liquid, preventing the recording liquid from being sprayed stably and the nozzle from drying 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, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether and ethylene glycol monoethyl. Examples thereof include ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, and 4-methoxy-4-methylpentanone. 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 are used alone or as a mixture in the range of 2 to 50% by weight based on the total composition of the ink jet recording liquid. 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. As other additives, urea, dimethyl urea and the like can be added.

When the printing medium of the recording liquid is like paper,
A penetrant can be added to speed up the penetration of the recording liquid into the paper and 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, printing bleeding and paper loss (print-through) occur, which is not preferable.

The preservative is used to prevent the decay of recording liquid and the generation of mold, and includes sodium dehydroacetate, sodium benzoate, sodium pyridinethione {1} oxide,
Amine salts of zinc pyridinethione {1} oxide, 1,2-benzisothiazoline-3-one, 1-benzisothiazoline-3-one, and the like are used. These are preferably used at about 0.05 to 1.0% by weight of the recording liquid. The chelating agent blocks metal ions in the recording liquid, and prevents metal deposition at the nozzle portion and insoluble substances in the recording liquid, etc., and ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid Acid sodium salt, ethylenediaminetetraacetic acid diammonium salt, ethylenediaminetetraacetylic acid tetraammonium salt, etc.
It is preferable to use 005 to 0.5% by weight.

Further, in order to adjust the pH of the recording liquid to a desired pH and obtain the stability of the recording liquid or the stability with the recording liquid pipe in the recording apparatus, an adjusting agent such as an amine, an inorganic salt or ammonia, phosphorus A buffer such as an acid can be used. Also,
An antifoaming agent may be added to prevent the circulation or movement of the recording liquid and the generation of bubbles during the production of the recording liquid.

The simplest method of producing the recording liquid of the present invention is to mix a pigment and a pigment dispersant into a dispersion or solution of an aqueous resin, or a surfactant solution. Alternatively, it is added to a slurry of water or a solvent of the pigment and adsorbed on the surface of the pigment. During the process, a pigment composition obtained by a method of adding a powder or a solution or a dispersion of a pigment dispersant, adsorbing the pigment on the surface of the pigment, and optionally drying after filtration may be added to the aqueous resin dispersion or solution. it can. In order to disperse the pigment or the pigment composition in the aqueous resin dispersion or solution, it is preferable to use a disperser such as a paint shaker, a ball mill, an attritor, a sand mill, or a jet mill.

The pigment, the pigment dispersant and the aqueous resin or surfactant may be kneaded well in advance with a kneader or a two-roll mill, and then further dispersed with a disperser such as a sand mill or an attritor. In this case, the pigment content is 10 to 50% by weight, preferably 10 to 30% by weight,
It is preferable to use a pigment concentrate containing 2.5 to 20% by weight of an aqueous resin and / or a surfactant. The dispersion thus obtained is appropriately diluted with water and mixed with necessary additives. The mixed recording solution is filtered with a filter having a pore size of 1.0 μm or less before or after dilution. Preferably, the solution is filtered with a filter of 0.45 μm or less. Prior to filtration of the filter, filtration by centrifugation can be used, which reduces clogging in filtration by the filter and facilitates filter replacement. The recording liquid has a viscosity of 0. 0 depending on the type of the recording apparatus.
Adjust as a liquid at 8-15 cps (25 ° C.). The surface tension is 25 to 60 dyn / cm. Although the PH is not particularly limited, it is in the range of 4 to 12, and preferably
A weak alkalinity of 7 to 9 is preferred.

Since the recording liquid produced by the present invention is water-based and has extremely good water resistance, it is suitably used as an ink-jet recording liquid. It can be used in fields such as marking, numbering, and barcode. In addition, 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 recorded matter can be formed. Table 1 shows typical examples of the compound represented by the general formula (1).

[0023]

[Table 1]

[0024]

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] The following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated liquid of an aqueous dispersion ink jet recording liquid. Lionol Blue FG-7330 (pigment manufactured by Toyo Ink Mfg. Co., Ltd.) 19.0 parts Joncryl 61J (styrene acrylic copolymer solid content 31.0% manufactured by Johnson Polymer Co., Ltd.) 16.4 parts Emulgen A-90 (nonionic 5.0 parts Pigment dispersant a 1.0 part Ion-exchanged water 58.6 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is added as appropriate to obtain a viscosity of 2 parts. .5c
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 12.5 parts of the above concentrated liquid Emmapoly TYN-40 (44.8% styrene acrylic copolymer solid content, manufactured by Gifu Shellac Works) 5.5 parts Glycerin 10.0 parts Ion-exchanged water 72.0 parts

Examples 2 to 4 Water-dispersed inkjet recording liquids were prepared in the same manner as in Example 1 except that the compounds b to d were used.

Example 5 The following ingredients were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous inkjet recording liquid. Hostaperm Pink E (manufactured by Pigment Hoechst) 19.4 parts Joncryl 62 (34.0% solid content of styrene acrylic copolymer manufactured by Johnson Polymer) 14.7 parts Emulgen A-90 5.0 parts Pigment dispersant e 0 .6 parts Ion-exchanged water 60.3 parts The above concentrate and the following were mixed, and diethylene glycol monobutyl ether was added as appropriate to give a viscosity of 2.5 c.
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 12.5 parts of the above concentrated liquid 5.5 parts of Emapoly TYN-40 5.5 parts of glycerin 10.0 parts of ion-exchanged water 72.0 parts

Examples 6 to 8 Water-dispersed inkjet recording liquids were prepared in the same manner as in Example 5 except that the compounds f to h were used.

Example 9 The following materials were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous ink-jet recording liquid. Hansa Brilliant Yellow 5GX02 (Pigment Hoechst) 19.0 parts Joncryl 62 8.8 parts Emulgen A-90 7.0 parts Pigment dispersant i 1.0 part Ion-exchanged water 64.2 parts The above concentrated solution and the following And diethylene glycol monobutyl ether as appropriate, and a viscosity of 2.5 c
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 12.5 parts of the above concentrated liquid 5.5 parts of Emapoly TYN-40 5.5 parts of glycerin 10.0 parts of ion-exchanged water 72.0 parts

Example 10 Compound j according to Example 9
Was used to prepare a water-dispersed inkjet recording liquid. Example 11 The following materials were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous ink-jet recording liquid. Irgazine Yellow 2GLTE (Pigment manufactured by Ciba) 19.0 parts Joncryl 62 8.8 parts Emulgen A-90 7.0 parts Pigment dispersant k 1.0 part Ion-exchanged water 64.2 parts And diethylene glycol monobutyl ether as appropriate, and a viscosity of 2.5 c
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 12.5 parts of the above concentrated liquid 5.5 parts of Emapoly TYN-40 5.5 parts of glycerin 10.0 parts of ion-exchanged water 72.0 parts

Example 12 A water-dispersed inkjet recording liquid was prepared in the same manner as in Example 11, except that Compound 1 was used. Example 13 The following raw materials were mixed and dispersed for 24 hours using a paint shaker to prepare a water-dispersed inkjet recording liquid concentrate. Hosta Palm Violet RL Special (Pigment Hoechst) 14.5 parts Joncryl 61J 16.1 parts Emulgen A-90 5.0 parts Pigment dispersant m 1.5 parts Ion-exchanged water 62.9 parts The above concentrated solution and the following And diethylene glycol monobutyl ether is added as appropriate to give a viscosity of 2.5 c.
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 15.0 parts of the above concentrated solution 5.5 parts of emapoly TYN-40 5.5 parts of glycerin 10.0 parts of 69.5 parts of ion-exchanged water [Example 14] A water-dispersed inkjet recording liquid was prepared using compound n according to Example 13. did.

Example 15 The following materials were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous inkjet recording liquid. Monarch 800 (Pigment Cabot) 14.5 parts Joncryl 61J 16.1 parts Emulgen A-90 5.0 parts Pigment dispersant a 1.5 parts Ion-exchanged water 62.9 parts The above concentrated solution and the following: , And diethylene glycol monobutyl ether is added as appropriate to give a viscosity of 2.5 c.
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 15.0 parts of the above concentrated liquid 5.5 parts of Emapoly TYN-40 5.5 parts of glycerin 10.0 parts of ion-exchanged water 69.5 parts

Comparative Example 1 The following raw materials were mixed and dispersed for 12 hours using a paint shaker to prepare a concentrated aqueous inkjet recording liquid. Lionol Blue FG-7330 0.0 parts Joncryl 61J 16.4 parts Emulgen A-90 5.0 parts ion-exchanged water 58.6 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is added as appropriate. In addition, viscosity 2.5c
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 12.5 parts of the above concentrated liquid 5.5 parts of Emapoly TYN-40 5.5 parts of glycerin 10.0 parts of ion-exchanged water 72.0 parts

Comparative Example 2 The following raw materials were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous inkjet recording liquid. Hostaperm Pink E 20.0 parts Joncryl 62 14.7 parts Emulgen A-90 5.0 parts Ion-exchanged water 60.3 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is added as appropriate. Viscosity 2.5c
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 12.5 parts of the above concentrated liquid 5.5 parts of Emapoly TYN-40 (44.8% solid content of styrene acrylic copolymer, manufactured by Gifu Shellac Works) Glycerin 10.0 parts Ion-exchanged water 72.0 parts

Comparative Example 3 The following ingredients were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous inkjet recording liquid. Hansa Brilliant Yellow 5GX02 20.0 parts Joncryl 62 8.8 parts Emulgen A-90 7.0 parts Ion-exchanged water 64.2 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is added as appropriate. , Viscosity 2.5c
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 12.5 parts of the above concentrated liquid 5.5 parts of Emapoly TYN-40 5.5 parts of glycerin 10.0 parts of ion-exchanged water 72.0 parts

Comparative Example 4 The following raw materials were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous inkjet recording liquid. Irgazine Yellow 2GLTE 20.0 parts Joncryl 62 8.8 parts Emulgen A-90 7.0 parts ion-exchanged water 64.2 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is added as appropriate. , Viscosity 2.5c
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 15.0 parts of the above concentrated liquid 5.5 parts of Emapoly TYN-40 5.5 parts of glycerin 10.0 parts of ion-exchanged water 69.5 parts

Comparative Example 5 The following materials were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous ink-jet recording liquid. Hosta Palm Violet RL Special 16.0 parts Joncryl 61J 16.1 parts Emulgen A-90 5.0 parts ion-exchanged water 62.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is added as appropriate. 2.5c viscosity
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 15.0 parts of the above concentrated liquid 5.5 parts of Emapoly TYN-40 5.5 parts of glycerin 10.0 parts of ion-exchanged water 69.5 parts

Comparative Example 6 The following ingredients were mixed and dispersed for 24 hours using a paint shaker to prepare a concentrated aqueous inkjet recording liquid. Monarch 800 16.0 parts Joncryl 61J 16.1 parts Emulgen A-90 5.0 parts Ion-exchanged water 62.9 parts The above concentrate and the following are mixed, and diethylene glycol monobutyl ether is added as appropriate to obtain a viscosity. 2.5c
ps (25 ° C.) and surface tension were adjusted to 40 dyn / cm. Thereafter, the mixture was filtered using a 1.0 μm membrane filter and further filtered using a 0.45 μm membrane filter to prepare a water-dispersed inkjet recording liquid. 15.0 parts of the above concentrated liquid 5.5 parts of Emapoly TYN-40 5.5 parts of glycerin 10.0 parts of ion-exchanged water 69.5 parts

The storage stability of the aqueous dispersion ink-jet recording liquids prepared according to Examples 1 to 14 and Comparative Examples 1 to 6 was examined by examining the presence or absence of sedimentation of the pigment and the change in viscosity as to the storage stability, and filled in a cartridge of HG5130 manufactured by Epson Corporation. Print out,
The clogging was tested. Storage stability Take 30 cc of the recording solution into a screw cap bottle (Nidec Rika Glass Co., Ltd.) and leave it at 60 ° C. for 1 month. Then, check for sedimentation of the pigment and check the type B viscometer (Tokyo Keiki Co., Ltd.) At 25 ° C
Was measured. No pigment sedimentation ○ Pigment sedimentation × Viscosity No change in viscosity ○ Slightly thickening △ Thickening ×

Clogging properties Continuous one-hour stamping was performed to check for clogging. No clogging occurred. ○ Clogging occurred 15 to 30 minutes after the start of stamping. △ Clogging occurred within 15 minutes after starting stamping. Table 2 shows the evaluation results.

[0040]

[Table 2]

According to the present invention, it is possible to obtain a 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 possible to expand the use of the aqueous recording liquid, which often has a shortage of water resistance due to the influence of the conventional recording medium.

Continuation of the front page (56) References JP-A-61-12768 (JP, A) JP-A-6-316676 (JP, A) JP-A-6-345997 (JP, A) JP-A-56-166266 (JP) , A) JP-A-56-167267 (JP, A) JP-A-56-167762 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00-11/20 C09B 67/20 C09D 17/00

Claims (4)

(57) [Claims] 1. The ink composition of claim 1, wherein the composition is based on the entire composition.
And 0.5 to 10% by weight of pigment, 0.1 to 10 % of aqueous resin
% Of a surfactant, 0.1 to 10 % by weight of a surfactant and 0.001 to 5% by weight of a pigment dispersant represented by the general formula (1).
Ink-jet recording liquid according to claim Mukoto. General formula (1) P- [XYZN (R ¹ ) R ² ] n (where P is an organic dye residue or a heterocyclic residue , X
It is _{-SO 2 -, - CO -,} - CH 2 -, - O -, - CO
A divalent linking group selected from O-, -NH- or a combination thereof, Y is a direct bond or -N (R)-(where R is H or an alkyl group having 1 to 18 carbon atoms or ZN ( R
¹ ) R ² ) or —O— or Z is an alkylene group having 1 to 6 carbon atoms, R ¹ and R ² are each independently an optionally substituted alkyl group having 1 to 18 carbon atoms or R ¹ and R ^{And 2 represent an} optionally substituted heterocyclic ring which may contain N, O or S, and n represents an integer of 1 to 3, respectively. ) 2. A further ink jet recording liquid of claim 1 wherein the aqueous solvent containing 2 to 50% by weight of the total composition of the inkjet recording liquid as a reference. 3. An ink jet recording liquid according to claim 1 or 2 wherein the aqueous resin is an acrylic copolymer resin. 4. A pigment containing a pigment, a pigment dispersant represented by the general formula (1) and an aqueous resin or a surfactant in an amount of 10 to 5%.
After the 0 wt% pigment concentrate was dispersed in water and diluted to a predetermined pigment concentration claims 1, characterized in that filtered with following filters pore size 1.0 .mu.m 3 or <br/> The method for producing a recording liquid for inkjet according to the above.