JP3191615B2 - Recording liquid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a recording liquid. More specifically, the present invention relates to an aqueous pigment type recording liquid for ink jet printing having excellent stability and printing characteristics.

[0002]

2. Description of the Related Art Conventionally, aqueous inkjet inks have been used in which various water-soluble dyes are dissolved in an aqueous medium and various additives are added as necessary. The following items are particularly important as items required for the inkjet ink. (1) A high-quality recorded image without blurring can be obtained. (2) The drying and fixing speed of the ink is high. (3) Ink can be stably ejected without clogging in the nozzles and ink distribution channels. (4) The storage stability of the ink is good. (5) The recording density is high. (6) The printed matter has good weather resistance and water resistance.

Specifically, as disclosed in JP-A-53-61412, JP-A-54-89811, and JP-A-55-65269, acid dyes, direct dyes, An ink in which a water-soluble dye such as a basic dye is dissolved in an aqueous solvent has been often used. However, as the water-soluble dye, a dye having high solubility in water is used in order to obtain the stability of the recording liquid, and there is a problem that the water resistance of the ink jet recorded matter is poor. On the other hand, to improve water resistance,
As disclosed in JP-A-56-57862, attempts have been made to change the structure of a dye or to prepare a recording solution having a strong basicity. Also, JP-A-50-49004, JP-A-57-366
No. 92, JP-A-59-20696 and JP-A-59-146889, attempts to improve the water resistance of a recorded material by utilizing the reaction between a recording paper and a recording liquid. Has been made.

Although these methods are effective for certain types of recording paper, various types of recording paper are used in the ink jet system, so that not all recording papers have sufficient water resistance. The ink drying property was not satisfactory. Attempts have been made to add polymer emulsions to inks for the purpose of improving bleeding and water resistance. For example, JP-A-54-58504 and JP-A-54-146109 disclose swelling and impregnating an oily dye in a polymer emulsion, and JP-A-55-18412 discloses a polymer emulsion containing a polymer emulsion. , JP 6
Japanese Patent Application Laid-Open No. 2-184072 discloses a method of reacting a dye with a cross-linked emulsion, Japanese Patent Application Laid-Open No. 3-6270 discloses a method containing a cross-linked emulsion, and Japanese Patent Application Laid-Open No. 3-160068 discloses a method containing an MFT emulsion of 40 ° C. or higher. Japanese Patent Application Laid-Open No. 3-250069 discloses a method using an emulsion dyed with a dye.

[0005] However, these inks basically use a dye, and although they have a certain effect on water resistance and light resistance, they are not satisfactory. Further, in general, polymer emulsions have a problem that clogging is likely to occur in ink passages and nozzles of an ink jet printer. From the above, water resistance,
As a coloring component having excellent light fastness, an ink using a pigment is promising and various studies have been made. However, the pigment alone does not have a fixing property on a recording paper or an OHP sheet, and it is necessary to use a binder resin. However, there was no polymer emulsion which was free from clogging, had good water resistance and light resistance, and gave high resolution to printed matter.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a water-based pigment-type recording liquid having excellent physical properties as an ink-jet ink, particularly having excellent water resistance, light resistance and resolution, and without clogging at a nozzle. To provide.

[0007]

That is, the present invention relates to 1 to 10% by weight of an anionic group-containing monomer, 0.5 to 5% by weight of a nonionic water-soluble monomer and 85 to 98.5% of another monomer.
A water-dispersible resin composition obtained by emulsion polymerization of 100 parts by weight of a polymerizable monomer containing 0.1% by weight in the presence of 0.1 to 10 parts by weight of an anionic surfactant and 0.1 to 5 parts by weight of colloidal silica solids ( A recording liquid comprising A) and a pigment (B).

The anionic group-containing monomer is a compound having both an ethylenically unsaturated double bond and an anionic group such as a carboxyl group and a sulfonic acid group. Specifically, acrylic acid, methacrylic acid, Examples include itaconic acid, fumaric acid, maleic acid, and 3-sulfopropyl acrylate. The anionic group-containing monomer is contained in the polymerizable monomer in an amount of 1 to 10% by weight. If the amount is less than 1% by weight or more than 10% by weight, the stability of the water-dispersible resin composition (A) obtained at the same time may be impaired, and the recording liquid may be clogged at the head portion.

Examples of the nonionic water-soluble monomer include hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, (meth) acrylamide, and N-methylol (meth).
Examples include acrylamide such as acrylamide and di-N-methylol (meth) acrylamide, derivatives thereof, and polyethylene glycol (meth) acrylate. The nonionic water-soluble monomer is 0.5 to 5 in the polymerizable monomer.
% By weight. If the amount is less than 0.5% by weight or more than 5% by weight, the stability of the water-dispersed resin composition (A) obtained at the same time may be impaired, and the recording liquid may be clogged at the head portion.

Other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acryl (Meth) such as lauryl acrylate, stearyl (meth) acrylate
Examples include alkyl acrylate, styrene, methyl styrene, vinyl toluene, vinyl acetate, and acrylonitrile. Reactive monomers such as glycidyl (meth) acrylate and acrolein, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and polyethylene glycol di (meth) acrylate And polyfunctional monomers such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate.

Examples of the anionic surfactant include, for example,
Sodium lauryl sulfate ("Emal O" manufactured by Kao Corporation)
"Emal 10" etc.), higher alcohol sodium sulfate ("Emal 40" manufactured by Kao Corporation), sodium dodecylbenzene sulfonate ("Neoperex No.6" manufactured by Kao Corporation),
"Neoperex F-65" etc.), sodium alkylnaphthalenesulfonate ("Perex NB-L" manufactured by Kao Corporation),
Sodium dialkylsulfosuccinate (Kalex "Perex OT-P", "Perex CS", etc.), sodium alkyl diphenyl ether disulfonate (Kao "Perex SS-L" etc.), sodium polyoxyethylene alkyl ether sulfate (Kao “Emal 20C”, “Levenol WX”, etc.), sodium salt of β-naphthalenesulfonic acid formalin condensate (“Demol RN” manufactured by Kao Corporation)
Etc.).

As the colloidal silica, it is preferable to use an aqueous dispersion type. Dried solid colloidal silica is difficult to re-disperse and stably exist in water, and is not suitable for use. As water-dispersed colloidal silica, for example, "Ludox A" manufactured by DuPont
M ”,“ Snowtex O ”,“ Snowtex N ”,“ Snowtex C ”,“ Snowtex ”
20 ”and the like. Among them, colloidal silica having a particle size of 0.4 μm or less, more preferably 0.1 μm or less is preferred. If the particle size is large, the nozzle may be clogged.

The water-dispersed resin composition (A) is composed of 100 parts by weight of the above polymerizable monomer, 0.1 to 10 parts by weight of an anionic surfactant, and 0.1 to 5 parts by weight of solid colloidal silica in an aqueous medium.
It is obtained by emulsifying and suspending parts by weight and, if necessary, a nonionic surfactant, an antifoaming agent, etc., and then adding a water-soluble thermal polymerization initiator under heating to carry out thermal polymerization. If the amount of the anionic surfactant is less than 0.1 part by weight, the stability of the obtained water-dispersed resin composition (A) is deteriorated, so that the storage stability of the recording liquid is deteriorated and the head is clogged. There is fear. On the other hand, when the amount exceeds 10 parts by weight, the surface tension of the obtained recording liquid is remarkably reduced, the recording liquid droplets discharged from the nozzles become mist, and the resolution is reduced and the head is stained.

The amount of colloidal silica used is 0.1
When the amount is less than the weight part, the resolution of the recorded matter is deteriorated. On the other hand, when the amount exceeds 5 parts by weight, the obtained water-dispersed resin composition (A) lacks stability, so that the storage stability of the recording liquid may deteriorate or clogging may occur. The particle shape and the particle size of the water-dispersed resin composition (A) can be variously changed by a polymerization operation, an activator, and the like.
Particles having a particle size of about to several μm are obtained. The particle size is preferably 0.4 μm or less, more preferably 0.2 μm or less, in order to eliminate clogging of the recording liquid at the nozzle.

The water-dispersed resin composition (A) is preferably incorporated in the recording liquid in a solid content of 0.2 to 10% by weight, more preferably 0.5 to 5% by weight. If the amount is less than 0.2 parts by weight, the fixability of the pigment to paper or an OHP sheet deteriorates,
If it exceeds 10% by weight, the storage stability of the recording liquid will deteriorate,
Head clogging also occurs.

As the pigment (B), various pigments used for printing inks, paints and the like 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 orange pigments 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 (indicated by a color index (CI) number).

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 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 centrifugal sedimentation.
It is 0.2 μ or less, more preferably 0.1 μ or less. With such a particle size, the filtration operation in the production of the recording liquid is easy, and the sedimentation of the 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.

The water-dispersible resin composition (A) and the pigment (B) are dispersed in water to form a recording liquid. When preparing the recording liquid, a dye, an aqueous solvent, a penetrant, Fungicides, chelating agents, pH adjusters, defoamers, surfactants and the like can be added.

Dyes are used in such a manner that there is no problem in water fastness and light fastness for the purpose of adjusting hue, imparting concentration, 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 dyes, acid dyes, basic dyes, direct dyes,
Reactive dyes, disperse dyes, metal-containing dyes 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, and prevents 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, and ethylene glycol monoethyl ether. , 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-
Hexanetriol, tetrafurfuryl alcohol, 4-
Methoxy-4 methylpentanone and the like can be exemplified. Further, alcohols such as methanol, ethanol and isopropyl alcohol can be used for the purpose of speeding up 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.

When the printing medium of the recording liquid is a permeable material such as paper, a penetrant can be added 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 exemplified 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%, printing bleeding and paper loss (print-through) occur, which is not preferable.

The antifungal agent prevents the generation of mold in the recording liquid, and includes sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2 An amine salt of -benzisothiazolin-3-one, 1-benzisothiazolin-3-one and the like are used. These are used in the range of about 0.05 to 1.0% by weight of the recording liquid.

The chelating agent blocks the metal ions in the recording liquid and prevents the deposition of metal at the nozzle portion and the insoluble matter in the recording liquid, and the like. Ethylenediaminetetraacetic acid, ethylenediamine A sodium salt of tetraacetic acid, a diammonium salt of ethylenediaminetetraacetic acid, a tetraammonium salt of ethylenediaminetetraacetic acid, and the like are used. These are used in the range of 0.005 to 0.5% by weight of the recording liquid. 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, a pH adjuster such as an amine, an inorganic salt, or ammonia;
A buffer such as phosphoric acid can be used. Further, an antifoaming agent may be added in order to prevent circulation and movement of the recording liquid or generation of bubbles during production of the recording liquid.

Further, in order to improve the dispersion of the pigment, a surfactant such as an anionic, nonionic, cationic or amphoteric surfactant can be used. Examples of the anionic activator include fatty acid salts, alkyl sulfate salts, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates,
Alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalenesulfonic acid formalin condensate,
Examples thereof include polyoxyethylene alkyl phosphate ester 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, Examples 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 water-dispersed resin composition (A) is mixed with the pigment (B), water, and, if necessary, additives such as an aqueous solvent.
Disperse using a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, or the like. Alternatively, the water-dispersed resin composition (A) and the pigment (B) are kneaded well in advance with a kneader and a two-roll mill, and then further dispersed in a sand mill or the like, appropriately diluted with water, and other additives. To produce a recording liquid. Mixing and stirring can be performed by a high-speed disperser, emulsifier, or the like, in addition to stirring by a stirrer using ordinary blades.

Before or after dilution, the mixed recording liquid is preferably sufficiently filtered with a filter having a pore size of 0.65 μm or less, more preferably 0.45 μm or less. Prior to the filtration by filtration, filtration by centrifugation can also be performed, thereby reducing clogging in filter 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. Surface tension is 25-60 dyn / cm. The pH is not particularly limited, but is in the range of 4 to 12, and is preferably weakly alkaline of 7 to 9.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. In the examples, parts and% represent parts by weight and% by weight, respectively. (Production Example 1) The raw materials shown in Table 1 were charged at a ratio shown in Table 1 into a reactor and a dropping tank which had been saturated with N ₂ gas in advance. The polymerization reaction starts at 55-57 ° C and the temperature of the reactor is 59 ° C.
When it became, dripping was started. The dropping time was 100 minutes. The polymerization was carried out within a temperature range of 60 to 65 ° C., and the reaction was completed in about 3 hours. After that, pH 8 ~ with 25% ammonia water
9, to obtain a water-dispersed resin composition having a solid content of 20%.
The average particle size of the obtained water-dispersed resin composition was 120 nm as measured by a laser light scattering method.

[0030]

[Table 1] * 1 "Ludox AM" manufactured by DuPont (solid content 30%)

(Production Examples 2-3 and Comparative Production Examples 1-5)
Using the raw materials shown in Table 2, a solid content of 20
% Of an aqueous dispersion type resin composition was obtained. Table 2 shows the polymerization progress, the presence or absence of aggregates in the obtained aqueous dispersion type resin composition, and the average particle size.

[0032]

[Table 2]

Example 1 15 parts of carbon black ("MA-7" manufactured by Mitsubishi Kasei Co., Ltd.), 1.3 parts of an acrylic resin-based pigment dispersant ("F-157" manufactured by Nippon Polymer Industries Co., Ltd.), and a dispersion of a polyethylene oxide-based pigment Agent (“Emulgen 420” manufactured by Kao Corporation) 1.5
Parts, diethylethanolamine 0.1 part, glycerin 3
And 69.1 parts of purified water were dispersed in a sand mill for 2 hours to obtain an aqueous pigment dispersion. 25 parts of the obtained aqueous pigment dispersion, 10 parts of the water-dispersed resin composition obtained in Production Example 1, 10 parts of glycerin 10
, 0.15 parts of a fungicide (“Sodium Omazine” manufactured by Orin Chemical Co., Ltd.) and 54.85 parts of purified water were stirred and mixed with a disper, and then filtered through a 0.5 μm nitrocellulose membrane filter to obtain a black recording liquid. The obtained recording liquid was put into a cartridge of an ink jet printer (“THINKJET” manufactured by Hewlett-Packard Company) and recording was performed. As a result, a good printed matter was obtained without clogging of the head. In addition, when water was dripped on the printed surface and the bleeding of the ink was examined, it was found that there was no bleeding and no flow of the ink, and that the ink had sufficient water resistance. Further, the obtained recording liquid did not change at all in printing characteristics even after storage at room temperature for 2 years and at 60 ° C. for 3 months.

(Example 2) 15 parts of a cyan pigment ("Lionol Blue FG7351" manufactured by Toyo Ink Mfg. Co., Ltd.) and an acrylic resin-based pigment dispersant ("PDX-6101" manufactured by Johnson Polymer Co., Ltd.)
1.5 parts, glycerin 5.0 parts and purified water 78.5 parts were dispersed in a sand mill for 2 hours to obtain an aqueous pigment dispersion. 20 parts of the obtained aqueous pigment dispersion, 10 parts of the water-dispersed resin composition obtained in Production Example 2, 10 parts of glycerin, 0.15 part of a fungicide ("Sodium Omazine" manufactured by Olin Chemical Co., Ltd.), and 59.85 parts of purified water After stirring and mixing with a disper, the mixture was filtered through a 0.5 μm nitrocellulose membrane filter to obtain a blue recording liquid. The obtained recording liquid is applied to an inkjet printer (“Inkjet Printer HG-513” manufactured by Seiko Epson Corporation).
0 "), and recording was performed. As a result, a good printed matter was obtained without clogging of the head. In addition, when water was dripped on the printed surface and the bleeding of the ink was examined, it was found that there was no bleeding and no flow of the ink, and that the ink had sufficient water resistance. Further, the obtained recording liquid did not change at all in printing characteristics even after storage at room temperature for 2 years and at 60 ° C. for 3 months.

Example 3 15 parts of yellow pigment ("Lionol Yellow 22-2845" manufactured by Toyo Ink Mfg. Co., Ltd.) and an acrylic resin-based pigment dispersant ("PDX-610" manufactured by Johnson Polymer)
1)) 1.5 parts, polyethylene oxide pigment dispersant (“Emulgen 920” manufactured by Kao Corporation) 1.5 parts, glycerin 5.0 parts,
77.0 parts of purified water was dispersed in a sand mill for 2 hours to obtain an aqueous pigment dispersion. 20 parts of the obtained aqueous pigment dispersion, Production Example 3
10 parts of the aqueous dispersion type resin composition obtained in 10 parts of glycerin,
Antifungal agent ("Sodium Omazine" manufactured by Olin Chemical Co., Ltd.)
After 0.15 part and 59.85 parts of purified water were stirred and mixed with a disper, the mixture was filtered through a 0.5 μm nitrocellulose membrane filter to obtain a yellow recording liquid. When recording was performed in the same manner as in Example 2 using the obtained recording liquid, a good printed matter was obtained without clogging of the head. In addition, when water was dripped on the printed surface and the bleeding of the ink was examined, it was found that there was no bleeding and no flow of the ink, and that the ink had sufficient water resistance. Furthermore, the obtained recording liquid is kept at room temperature for 2 years.
After printing at 60 ° C. for 3 months, there was no change in the printing characteristics.

(Example 4) 15 parts of a magenta pigment ("Posta Palm Pink E-02" manufactured by Hoechst), 1.5 parts of an acrylic resin-based pigment dispersant ("F-157" manufactured by Nippon Polymer Industries), polyethylene oxide 1.5 parts of a pigment dispersant (“Emulgen 920” manufactured by Kao Corporation), 5.0 parts of glycerin, and 77.0 parts of purified water were dispersed in a sand mill for 2 hours to obtain an aqueous pigment dispersion.
20 parts of the obtained aqueous pigment dispersion, 10 parts of the water-dispersed resin composition obtained in Production Example 1, 10 parts of glycerin, 0.15 part of a fungicide (“Sodium Omazine” manufactured by Olin Chemical Co., Ltd.), purified water
After stirring and mixing 59.85 parts with a disper, the mixture was filtered through a 0.5 μm nitrocellulose membrane filter to obtain a red recording liquid. When recording was performed in the same manner as in Example 2 using the obtained recording liquid, a good printed matter was obtained without clogging of the head. In addition, when water was dripped on the printed surface and the bleeding of the ink was examined, it was found that there was no bleeding and no flow of the ink, and that the ink had sufficient water resistance. Further, the obtained recording liquid did not change at all in printing characteristics even after storage at room temperature for 2 years and at 60 ° C. for 3 months.

(Comparative Example 1) 25 parts of an aqueous pigment dispersion obtained in the same manner as in Example 1, 10 parts of an aqueous dispersion type resin composition obtained in Comparative Production Example 1, 10 parts of glycerin, a fungicide ( 0.15 parts of “Sodium Omazine” manufactured by Olin Chemical Co., Ltd., purified water 5
After stirring and mixing 4.85 parts with a disper, filtration was attempted with a 0.5 μm nitrocellulose membrane filter, but the membrane filter was clogged with resin and could not be filtered.

Comparative Example 2 The procedure of Example 3 was repeated except that the water-dispersible resin composition obtained in Production Example 3 was replaced with the water-dispersible resin composition obtained in Comparative Production Example 4. A recording liquid was obtained. Using the obtained recording liquid, recording was performed in the same manner as in Example 2. When continuous printing was performed for 10 minutes, 30 of the 48 nozzles were clogged. Also, after printing for 1 hour after opening the head,
The nozzle portion dried and printing was not possible.

Comparative Example 3 The procedure of Example 4 was repeated except that the water-dispersed resin composition obtained in Production Example 1 was replaced with the water-dispersed resin composition obtained in Comparative Production Example 5. A recording liquid was obtained. Using the obtained recording liquid, recording was performed in the same manner as in Example 2. One hour after the head was opened, the resin adhered to the nozzle portion, and recording could not be performed. Also, 60 ℃
After storage for one month, a precipitate formed in the recording solution.

[0040]

The recording liquid of the present invention is water-based and has extremely good water resistance, so that it is suitably used as an ink-jet recording liquid. It can be used in fields such as marking, numbering, and barcode. Further, the light resistance is better than that of the dye type recording liquid, and a color image having excellent preservation property of recorded matter can be formed.

Continuation of the front page (56) References JP-A-51-131554 (JP, A) JP-A-55-9623 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11 / 00-11/20

Claims (7)

(57) [Claims] 1. An anionic group-containing monomer in an amount of 1 to 10% by weight,
100 parts by weight of a polymerizable monomer containing 0.5 to 5% by weight of a nonionic water-soluble monomer and 85 to 98.5% by weight of another monomer, 0.1 to 10 parts by weight of an anionic surfactant and 0.1 to 5 parts by weight of colloidal silica solids A recording liquid comprising a water-dispersible resin composition (A) and a pigment (B) obtained by emulsion polymerization in the presence of parts. 2. An anionic group-containing monomer, wherein the anionic group is a carboxyl group or a sulfonic group.
The recording solution described in the above. 3. The recording liquid according to claim 1, wherein the nonionic water-soluble monomer is a hydroxyl group-containing monomer. 4. The nonionic water-soluble monomer is one or a mixture of two or more selected from acrylamide, methacrylamide, N-substituted methylol group-containing acrylamide derivatives, and N-substituted methylol group-containing methacrylamide derivatives. Item 3. The recording liquid according to Item 1 or 2. 5. The non-ionic water-soluble monomer is a (meth) acrylate-terminated polyethylene glycol.
Or the recording solution according to 2. 6. The recording liquid according to claim 1, wherein the colloidal silica is an aqueous dispersion having a particle size of 0.4 μm or less. 7. A water-dispersed resin composition (A) having a solid content of 0.2
The recording liquid according to any one of claims 1 to 6, wherein the content of the recording liquid is from 10 to 10% by weight.