JP2000290565A - Recording liquid for ink jet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stable recording liquid excellent in mildew resistance by compounding a coloring material, a water-soluble or water-dispersible mildew- proofing agent containing allyl mustard oil and water. SOLUTION: The title recording liquid comprises 0.5-10 wt.% of a coloring material such as a dye such as a direct dye, a reactive dye or the like, a pigment or the like, 0.01-10 wt.%, in terms of allyl mustard oil, of a water-soluble or water-dispersible mildew-proofing agent, 50-90 wt.% of water, and further a water-soluble organic solvent, 1-15 wt.% of a viscosity modifier such as a polyvinyl alcohol or the like, a surfactant, an amphipathic agent, a pH adjusting agent, a chelating agent and the like. The amount of the water-soluble organic solvent contained is not more than 10 wt.% in case of a monohydric alcohol, 5-30 wt.% in case of a polyhydric alcohol, 5-20 wt.% in case of a polyhydric alcohol ether, not more than 10 wt.% in case of a cyclic amide and 5-40 wt.% for the whole organic solvent. As the surfactant are preferable a nonylphenyl polyethylene glycol ether and other nonionic surfactants and the surface tension of the recording liquid is set to 30-50 dyne/cm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording liquid used in an ink jet recording apparatus such as an ink jet printer, and more particularly, to an improvement in the antifungal property of the ink jet recording liquid without impairing its performance. The present invention relates to an inkjet recording liquid.

[0002]

2. Description of the Related Art Oily or aqueous recording liquids have conventionally been used as recording liquids for ink jet recording apparatuses such as ink jet printers.

[0003] In general, a commonly used recording liquid for ink-jet does not always have sufficient antifungal properties. In addition, there is a problem that mold is generated, the liquid flow path and the nozzle in the apparatus are clogged, and the color of the recording liquid is changed by the action of the mold.

On the other hand, as an aqueous recording liquid used in an ink jet recording apparatus, Japanese Patent Publication No. Sho 62-3435 has been proposed.
As disclosed in Japanese Patent Publication No. 0 and Japanese Patent Publication No. 2-12266, there is known an aqueous ink jet recording ink containing a water-soluble dye, a fungicide, and water.

However, when the fungicides described in the above publications or fungicides such as imidazole-based thiabenzol (manufactured by US Merck) and Melgar BCM (manufactured by Hoechst) are used, those having a high fungicidal effect cannot be obtained. , Because of its toxicity
There have been problems such as a problem in safety and a decrease in performance of the recording liquid.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in an ink jet recording liquid used in an ink jet recording apparatus such as an ink jet printer.

That is, according to the present invention, in the above-described ink jet recording liquid, molds are generated in the recording liquid to cause clogging of the liquid passages and nozzles in the ink jet apparatus, and the color of the recording liquid is reduced. Does not change, and as with the case of using a general antifungal agent, the toxicity of the recording liquid is increased, causing a problem in safety, and the performance of the recording liquid is also reduced. In addition, the present invention provides an inkjet recording liquid having excellent antifungal properties and capable of performing stable inkjet recording.

[0008]

According to the present invention, in order to solve the above-mentioned problems, an ink jet recording liquid containing at least a coloring material, a water-soluble or water-dispersible fungicide, and water is provided. Allyl mustard oil was included as the above-mentioned fungicide.

[0009] In order to impart a fungicidal property by including a water-soluble or water-dispersible fungicide in the recording liquid, as in the ink-jet recording liquid of the present invention, the above-mentioned allyl mustard oil is used. As in the case of using a general antifungal agent, the toxicity of the recording liquid is increased and there is no problem in safety, and the performance of the recording liquid does not decrease, and the generation of mold in the recording liquid does not occur. Sufficiently suppressed, when used in an ink jet recording apparatus, without clogging of the liquid flow path and nozzles, and without changing the color of the recording liquid, so that stable ink jet recording can be performed Become.

When the above-mentioned allyl mustard oil is contained in the recording liquid as a fungicide as described above, if the amount is small, a sufficient fungicidal effect cannot be obtained, but the amount becomes too large. Since the drying property of the recording liquid is deteriorated and the fixing property of the recording liquid to the recording paper or the like is deteriorated,
Preferably, the above-mentioned allyl mustard oil is contained in the recording liquid in a range of 0.01 to 10% by weight, more preferably, 0.1 to 5% by weight in the recording liquid. I do.

Here, as the coloring material used in the ink jet recording liquid in the present invention, conventionally known various dyes such as acid dyes, direct dyes, basic dyes and reactive dyes, and various pigments are used. Usually, such a coloring material is contained in the recording liquid in an amount of 0.5 to 10% by weight, preferably 2 to 6% by weight.

The amount of water used as a solvent for the antifungal agent and the coloring material is such that the amount of water in the recording liquid is 50 to 90% by weight, preferably 70 to 90% by weight.

Further, in the ink jet recording liquid, in addition to the coloring material, the antifungal agent and water, a water-soluble organic solvent, a viscosity modifier, a surfactant, An amphiphile, a pH adjuster, a chelating agent and the like can be added, and if necessary, an oxygen absorber, a rust inhibitor, a quencher and the like can be added.

When a water-soluble organic solvent is added to the recording liquid, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, or the like may be used to enhance the drying property of the recording liquid and improve the fixing property of the recording liquid. Add monohydric alcohol such as isopropyl alcohol,
For example, polyalkylene glycols such as polyethylene glycol and polypropylene glycol and alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol are used to improve the moisture retention of the recording liquid and adjust the viscosity and surface tension. Alkylene glycols having 2 to 6 carbon atoms, polyhydric alcohols such as glycerin and glycerol, and, for example, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene Polyhydric alcohol ethers such as glycol butyl ether may be added.
For the purpose of enhancing corrosion resistance and preventing clogging in a nozzle or the like, for example, cyclic amides such as 2-pyrrolidone and 1 (N) -methyl-2-pyrrolidone can be used.

When these water-soluble organic solvents are contained in the recording liquid, the content of the monohydric alcohol is 10% by weight or less, and the content of the polyhydric alcohol is 5% or less. -30% by weight, preferably 5-1
0% by weight, in the case of polyhydric alcohol ethers, the content is 5 to 20% by weight, preferably 5 to 10% by weight, and in the case of cyclic amides, the content is 10% by weight or less, preferably 2% by weight or less. The total amount of these organic solvents is 5 to 40% by weight in the recording liquid, preferably 5 to 25% by weight.
% By weight.

As the viscosity adjusting agent to be added to the above-mentioned recording liquid, generally known ones can be used as long as they do not adversely affect the above-mentioned coloring material and water-soluble organic solvent. , Polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, water-soluble acrylic resin, polyvinyl pyrrolidone, gum arabic,
Dextrin, casein, peptin, and the like can be used. When such a viscosity modifier is contained in the recording liquid, the content becomes 1 to 15% by weight, preferably 2 to 10% by weight. To do.

Further, in order to suppress the bleeding of the recording liquid and to stabilize the ejection property from the nozzle of the ink jet recording apparatus, a surfactant is added to the recording liquid to reduce the surface tension of the recording liquid to 30 to 50 dyne / cm (liquid). (Temperature of 25 ° C.).

The surfactant to be added to the recording liquid may be any of nonionic, anionic and cationic surfactants, but anionic or cationic surfactants are added. In this case, salt tends to precipitate,
Preferably, a nonionic surfactant is added.

Here, as the nonionic surfactant, for example, a compound represented by the general formula C ₉ H ₁₉ C ₆ H ₄ O (CH ₂ CH ₂₎
O) nonyl phenyl polyethylene glycol ether represented by _n H, the formula _{C 8 H 17 C 6 H 4} O (CH 2 CH
₂ O) octylphenyl polyethylene glycol ethers represented by _n H, the general formula _{C 12 H 25 C 6 H 4} O (CH 2
CH ₂ O) dodecylphenyl polyethylene glycol ether represented by _n H, hydrocarbon-based nonionic surface active agents acetylene glycol ether such as shown in Chemical Formula 1 below, polyether modified silicone oil represented by 2 of the following Silicone-based nonionic surfactants such as
Formula _{C n F 2n + 1 O (} CH 2 CH 2 O) a nonionic surfactant of fluorine-based perfluoroalkyl polyoxyethylene ethanol represented by _m H can be used.

[0020]

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[0021]

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The anionic surfactants include:
For example, sodium lauryl alcohol sulfate, sodium dodecylbenzenesulfonate, modified carboxyl silicone oil, potassium perfluoroalkylcarboxylate, and the like can be used. As the cationic surfactant, for example, perfluoroalkyl quaternary Grade ammonium iodide and the like can be used.

When the above-mentioned surfactant is contained in the recording liquid, the surface tension of the recording liquid is 20 to 20.
The content is adjusted to 60 dyne / cm and the content of the surfactant to 2% by weight or less, preferably 0.05 to 1% by weight.

In order to prevent the precipitation of crystals in the recording liquid, an amphipathic agent is added to the recording liquid. Examples of the amphiphile include urea, amide, cyclic amide, and the like. Alkanolamine and the like can be used. When the amphiphile is contained in the recording liquid, the content is 2% by weight or less, preferably 0.2% by weight or less.
１1% by weight.

When the pH of the recording liquid is 8 or more, the generation of mold in the recording liquid is further suppressed. Therefore, a pH adjusting agent is added to the recording liquid to adjust the pH of the recording liquid to 8 or more. Preferably, the pH is adjusted to be in the range of 8 to 10.

The pH adjuster added to the above-mentioned recording liquid may be any known pH adjuster which can be controlled to a desired pH without adversely affecting the properties of the recording liquid.
Modifiers can be used, for example, amines such as monoethanolamine, diethanolamine and triethanolamine, hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, lithium carbonate,
Alkali metal carbonates such as sodium carbonate and potassium carbonate, hydroxides of alkaline earth metals such as calcium hydroxide, sodium tetraborate, ammonium hydroxide and the like can be used. In addition, when such a pH adjuster is added to the recording liquid, the pH of the recording liquid is adjusted to 8 as described above.
As described above, the content is adjusted to 1% by weight or less, preferably 0.1 to 0.3% by weight.

Further, in order to block metal ions in the recording liquid, a chelating reagent is added to the recording liquid,
As the chelating reagent, for example, sodium ethylenediaminetetraacetate, ethylenediaminetetraacetic acid, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramildiacetate, and the like can be used. When such a chelating reagent is contained in the recording liquid, the content is set to 1% by weight or less, preferably 0.1 to 0.5% by weight.

Further, if necessary, an oxygen absorbent such as sodium sulfite and sodium hydrogen sulfite, an acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, and pentaerythritol tetranitrate may be added to the above-mentioned recording solution. An additive such as a rust inhibitor such as dicyclohexylammonium nitrite and a quencher such as potassium iodide, potassium bromide and potassium chloride for preventing fading of the recording liquid are added. The amount of these additives to be added to the recording liquid is 1% by weight or less in the case of the oxygen absorber, and 1% by weight in the case of the rust preventive.
% By weight, preferably 0.3% by weight or less, and in the case of a quencher, 1% by weight or less.

[0029]

EXAMPLES Hereinafter, the ink jet recording liquid according to the examples of the present invention will be specifically described, and a comparative example will be given to demonstrate that the ink jet recording liquid in this example is excellent in terms of antifungal properties. Reveal.

(Example 1) In this example, 91.34% by weight of distilled water was used, and a black dye (PRO manufactured by Zeneca: PRO) was used.
3.9% by weight of JET FAST BK2), 0.01% by weight of allyl mustard oil as a fungicide, 2.2% by weight of diethylene glycol, 1.5% by weight of ethanol,
Sodium ethylenediaminetetraacetate was added in a ratio of 0.05% by weight and nonylphenyl polyethylene glycol ether in a ratio of 1.0% by weight. These were put into a beaker, heated and stirred at 45 ° C. for 1 hour, and the solution was stirred. After cooling, the mixture was filtered to obtain a black dye recording liquid.

Comparative Example 1 In this comparative example, the amount of distilled water in Example 1 was set to 91.35% by weight, while the addition of allyl mustard oil, a fungicide, was not carried out. In the same manner as in Example 1 above, a black dye recording liquid was obtained.

Example 2 In this example, 87.1% by weight of distilled water was used, and 3.9 of the same black dye as in Example 1 was used.
% By weight, 0.1% by weight of allyl mustard oil as a fungicide,
Triethylene glycol monobutyl ether is 4.8% by weight, ethanol is 3.0% by weight, sodium ethylenediaminetetraacetate is 0.3% by weight, and polyether modified silicone oil is 0.7% by weight. Except for the above, a black dye recording liquid was obtained in the same manner as in Example 1 above.

Example 3 In this example, the amount of distilled water in Example 2 was 87.0% by weight, the amount of allyl mustard oil as a fungicide was 0.2% by weight, and In the same manner as in Example 2 above, a black dye recording liquid was obtained.

Example 4 In this example, 83.6% by weight of distilled water was used, and 4.2% of the same black dye as in Example 1 was used.
% By weight, 2.7% by weight of allyl mustard oil as a fungicide,
Diethylene glycol monobutyl ether is 5.3% by weight, methanol is 3.2% by weight, sodium ethylenediaminetetraacetate is 0.4% by weight, and octylphenyl polyethylene glycol ether is 0.6% by weight. In the same manner as in Example 1 above, a black dye recording liquid was obtained.

Example 5 In this example, distilled water was 81.2% by weight, and the same black dye as in Example 1 was used in 4.2.
% By weight, 5.1% by weight of allyl mustard oil as a fungicide,
Diethylene glycol monobutyl ether is 5.3% by weight, methanol is 3.2% by weight, sodium ethylenediaminetetraacetate is 0.4% by weight, and octylphenyl polyethylene glycol ether is 0.6% by weight. In the same manner as in Example 1 above, a black dye recording liquid was obtained.

Example 6 In this example, 82.6% by weight of distilled water was used, and 3.9 of the same black dye as in Example 1 was used.
% By weight, 9.7% by weight of allyl mustard oil as a fungicide,
1.3% by weight of 2-pyrrolidone, 1.5% by weight of ethanol, 0.3% of sodium ethylenediaminetetraacetate
% By weight, and octylphenyl polyethylene glycol ether in a ratio of 0.7% by weight. Other than that, a recording solution of a black dye was obtained in the same manner as in Example 1 above.

Example 7 In this example, 81.8% by weight of distilled water was used, and 3.9 of the same black dye as in Example 1 was used.
% By weight, 10.5% by weight of allyl mustard oil as a fungicide, 1.3% by weight of 2-pyrrolidone, and 1.% by weight of ethanol.
5% by weight, 0.3% by weight of sodium ethylenediaminetetraacetate and 0.7% by weight of octylphenyl polyethylene glycol ether, and otherwise the same as in Example 1 described above. A recording solution of the dye was obtained.

Example 8 In this example, 91.34% by weight of distilled water was used, and a black dye (BaSF, manufactured by BASF) was used.
acid BK X38), 3.9% by weight, antifungal allyl mustard oil 0.01% by weight, diethylene glycol 2.2% by weight, ethanol 1.5% by weight, sodium ethylenediaminetetraacetate 0.05% by weight %, Nonylphenyl polyethylene glycol ether in an amount of 1.0% by weight, and the other conditions were the same as in Example 1 to obtain a black dye recording liquid.

Comparative Example 2 In this comparative example, the amount of distilled water in Example 8 was changed to 91.35% by weight, while allyl mustard oil as a fungicide was not added. In the same manner as in Example 8, a recording solution of a black dye was obtained.

Example 9 In this example, 87.1% by weight of distilled water was added to a cyan dye (manufactured by Bayer AG: BA
YSCRIPT CY BA) is 3.9% by weight, antifungal agent allyl mustard oil is 0.1% by weight, triethylene glycol monobutyl ether is 4.8% by weight, ethanol is 3.0% by weight, sodium ethylenediaminetetraacetate is A recording liquid of a cyan dye was obtained in the same manner as in Example 1 except that the ratio was 0.3% by weight and the polyether-modified silicone oil was 0.7% by weight.

Example 10 In this example, the amount of distilled water in Example 9 was 87.0% by weight, the amount of allyl mustard oil as a fungicide was 0.2% by weight, and In the same manner as in Example 9 above, a cyan dye recording liquid was obtained.

Example 11 In this example, 83.6% by weight of distilled water, 4.2% by weight of a magenta dye (AIZEN Acid Red 52, manufactured by Hodogaya Chemical Co., Ltd.), and allyl mustard oil as an antifungal agent 2.7% by weight, diethylene glycol monobutyl ether 5.3% by weight,
The proportions of methanol were 3.2% by weight, sodium ethylenediaminetetraacetate was 0.4% by weight, and octylphenyl polyethylene glycol ether was 0.6% by weight. Similarly, a recording liquid of a magenta dye was obtained.

Example 12 In this example, distilled water was 81.2% by weight, the same magenta dye as in Example 11 was 4.2% by weight, and allyl mustard oil, a fungicide, was 5.1.
% By weight, 5.3% by weight of diethylene glycol monobutyl ether, 3.2% by weight of methanol, 0.4% by weight of sodium ethylenediaminetetraacetate, and 0.6% by weight of octylphenyl polyethylene glycol ether. Otherwise, a magenta dye recording liquid was obtained in the same manner as in Example 1 above.

Example 13 In this example, 82.6% by weight of distilled water was used, and a yellow dye (manufactured by Bayer AG: BA
YSCRIPT YELLOW CA 51092) is 3.9% by weight, the fungicide allyl mustard oil is 9.7% by weight, 2-pyrrolidone is 1.3% by weight, ethanol is 1.5% by weight, and sodium ethylenediaminetetraacetate is 0%. A recording liquid of a yellow dye was obtained in the same manner as in Example 1 except that the ratio of octylphenyl polyethylene glycol ether was 0.7% by weight, and the other components were 0.3% by weight.

Example 14 In this example, 81.8% by weight of distilled water, 3.9% by weight of the same yellow dye as in Example 13, and 10.5% of allyl mustard oil as a fungicide were used.
% By weight, 1.3% by weight of 2-pyrrolidone, 1.5% by weight of ethanol, 0.3% by weight of sodium ethylenediaminetetraacetate, and 0.7% by weight of octylphenyl polyethylene glycol ether, Otherwise, a yellow dye recording liquid was obtained in the same manner as in Example 1 above.

Next, Examples 1 to 1 obtained as described above were used.
With respect to the recording liquids of the respective dyes of Comparative Example 4 and Comparative Examples 1 and 2, the mold resistance of these recording liquids was examined in accordance with the mold resistance test method of JIS Z 2911 specified in Japanese Industrial Standards. A 5 × 5 mm square solid image was printed on recording paper using the liquid, and after 30 seconds, the printed surface was rubbed with a urethane rubber blade to check the fixability of each recording liquid. These results, together with the oil content (% by weight), are shown in Table 1 below.

Here, in Table 1 below, regarding the mold resistance, ◎ indicates that no mold was generated, ○ indicates that almost no mold was generated, and X indicates that mold was generated.
Indicated by Regarding the fixability, 場合 indicates that there was no tailing from the printed portion to the blank portion, Δ indicates that slight tailing occurred, and X indicates that tailing occurred.

[0048]

[Table 1]

As a result, molds were generated in the recording liquids of the respective dyes of Comparative Examples 1 and 2 in which no antifungal agent, allyl mustard oil, was added. In the recording liquids of Nos. 14 and 14, the generation of mold was suppressed.

When the recording solutions of the dyes of Examples 1 to 14 were compared, the content of allyl mustard oil was 0.1%.
When the amount is more than 10% by weight, no mold is generated, and when used in an ink jet recording apparatus such as an ink jet printer, clogging does not occur in a liquid flow path or a nozzle in the apparatus, and the mold is not generated. The effect did not change the color of each recording liquid. Further, when the content of allyl mustard oil is 10% by weight or less, the fixing property of the recording liquid is less likely to be reduced, and tailing is prevented. In particular, the content of allyl mustard oil is 5% by weight or less. As a result, no tailing occurred and good fixability was exhibited. As a result, it was found that the content of allyl mustard oil in the recording liquid was preferably in the range of 0.1 to 10% by weight, and more preferably in the range of 0.1 to 5% by weight.

Example 15 In this example, 1.5% by weight of a styrene-acrylic acid-methyl acrylate copolymer having an acid value of 140 and a weight average molecular weight Mw of 5,000 and monoethanolamine of 1.15% were used. A mixture of 0% by weight, 5.0% by weight of diethylene glycol, and 71.5% by weight of distilled water was heated to 70 ° C. in a water bath to be dissolved, and carbon black (manufactured by Cabot Corporation: R250) at 20% by weight and isopropyl alcohol at 1% by weight, and the mixture was premixed for 30 minutes.

Then, a zirconium bead having a diameter of 1 mm was used as a pulverizing medium, and a sand mill (manufactured by Igarashi Kikai Co., Ltd.) with a filling rate of 50% by volume of the pulverizing medium was used. Was dispersed.

Next, the carbon black dispersion liquid thus dispersed was subjected to centrifugal separation at 12,000 rpm.
m, and centrifuged at 20 m for 20 minutes to remove coarse particles contained in the carbon black dispersion, thereby preparing a carbon black dispersion.

Then, 50.0% by weight of the carbon black dispersion thus prepared, 10.0% by weight of glycerin, 3.0% by weight of diethylene glycol, 5.0% by weight of N-methylpyrrolidone, isopropyl alcohol Was mixed with distilled water in an amount of 2.0% by weight, distilled water in an amount of 29.99% by weight, and an antifungal agent, allyl mustard oil, in an amount of 0.01% by weight to obtain a black pigment recording liquid.

Comparative Example 3 In this comparative example, the amount of the above-mentioned distilled water was reduced to 30.0% by weight in obtaining a black pigment recording liquid using the carbon black dispersion prepared in Example 15 above. On the other hand, a recording liquid of a black pigment was obtained in the same manner as in Example 15 except that allyl mustard oil as a fungicide was not added.

Example 16 In this example, the amount of the above-mentioned distilled water was 29.9% by weight in obtaining a black pigment recording liquid using the carbon black dispersion prepared in Example 15 above. A black pigment recording liquid was obtained in the same manner as in Example 15 except that the amount of allyl mustard oil as an antifungal agent was 0.1% by weight.

Example 17 In this example, the amount of the above-mentioned distilled water was 29.8% by weight in obtaining a black pigment recording liquid using the carbon black dispersion prepared in Example 15 above. A black pigment recording liquid was obtained in the same manner as in Example 15 except that the amount of allyl mustard oil as an antifungal agent was 0.2% by weight.

Example 18 In this example, in obtaining a black pigment recording liquid using the carbon black dispersion prepared in Example 15, the amount of distilled water was 27.3% by weight. A black pigment recording liquid was obtained in the same manner as in Example 15 except that the amount of allyl mustard oil as an antifungal agent was changed to 2.7% by weight.

Example 19 In this example, the amount of the above-mentioned distilled water was 24.9% by weight in obtaining a black pigment recording liquid using the carbon black dispersion prepared in Example 15 above. A black pigment recording liquid was obtained in the same manner as in Example 15 except that the amount of allyl mustard oil, a fungicide, was set to 5.1% by weight.

(Example 20) In this example, the amount of the distilled water was 24.9% by weight in obtaining a black pigment recording liquid using the carbon black dispersion prepared in Example 15 above. , Glycerin in an amount of 5.4% by weight, and an antifungal allyl mustard oil in an amount of 9.7% by weight.
Otherwise, a black pigment recording liquid was obtained in the same manner as in Example 15 above.

Example 21 In this example, the amount of the above distilled water was 24.9% by weight in obtaining a black pigment recording liquid using the carbon black dispersion prepared in the above Example 15. The amount of glycerin was set to 4.6% by weight, and the amount of allyl mustard oil as an antifungal agent was set to 10.5% by weight, except that the recording liquid of black pigment was obtained in the same manner as in Example 15 above. Was.

Example 22 In this example, a yellow pigment (Pigment Yellow 180) was used in place of the carbon black used in Example 15 above, and the other conditions were the same as in Example 15 above. A dispersion of a yellow pigment was prepared.

The dispersion of the yellow pigment thus prepared was 50.0% by weight, glycerin was 10.0% by weight,
3.0% by weight of diethylene glycol, 5.0% by weight of N-methylpyrrolidone and 2.
0 wt%, 29.9 wt% of distilled water, and 0.1 wt% of allyl mustard oil as a fungicide were mixed to obtain a yellow pigment recording liquid.

Example 23 In this example, the amount of the above-mentioned distilled water was 24.9% by weight in obtaining a yellow pigment recording liquid using the yellow pigment dispersion prepared in the above Example 22. %, The amount of allyl mustard oil as an antifungal agent was set to 5.1% by weight, and the other conditions were the same as in Example 22 to obtain a yellow pigment recording liquid.

Example 24 In this example, the amount of the above distilled water was 24.9% by weight in obtaining a yellow pigment recording liquid using the yellow pigment dispersion prepared in Example 22. %, The amount of glycerin is 4.6% by weight,
A yellow pigment recording liquid was obtained in the same manner as in Example 22 except that the amount of allyl mustard oil as an antifungal agent was 10.5% by weight.

COMPARATIVE EXAMPLE 4 In this comparative example, the amount of the above-mentioned distilled water was 30.0% by weight in obtaining a yellow pigment recording liquid using the yellow pigment dispersion prepared in the above Example 22. %, While preventing addition of allyl mustard oil as an antifungal agent.
In the same manner as in Example 2, a recording liquid of a yellow pigment was obtained.

Example 25 In this example, a magenta pigment (Pigment Red 7) was used in place of the carbon black used in Example 15 above, and the other conditions were the same as in Example 15 above. And a dispersion of a magenta pigment was prepared.

The dispersion of the magenta pigment thus prepared was 50.0% by weight, glycerin 10.0% by weight, diethylene glycol 3.0% by weight, N-methylpyrrolidone 5.0% by weight, isopropyl 2.0% by weight of alcohol, 29.9% by weight of distilled water and 0.1% by weight of allyl mustard oil as a fungicide were mixed to obtain a recording liquid of a magenta pigment.

(Example 26) In this example, the amount of distilled water was 24.9% by weight to obtain a recording liquid of magenta pigment using the dispersion liquid of magenta pigment prepared in Example 25. %, The amount of allyl mustard oil as an antifungal agent was set to 5.1% by weight, and otherwise, a recording liquid of a magenta pigment was obtained in the same manner as in Example 25.

(Example 27) In this example, the amount of distilled water was 24.9% by weight in obtaining a magenta pigment recording liquid using the magenta pigment dispersion prepared in Example 25. %, The amount of glycerin is 4.6
A magenta pigment recording liquid was obtained in the same manner as in Example 25, except that the amount of allyl mustard oil as an antifungal agent was 10.5% by weight.

(Comparative Example 5) In this comparative example, the amount of distilled water was 30.0% by weight in obtaining a recording liquid of magenta pigment using the dispersion liquid of magenta pigment prepared in Example 25. %, While preventing addition of allyl mustard oil as an antifungal agent, except that a recording liquid of a magenta pigment was obtained in the same manner as in Example 25.

Example 28 In this example, a cyan pigment (Pigment Blue 15) was used in place of the carbon black used in Example 15, and the other conditions were the same as in Example 15 above. A dispersion of a cyan pigment was prepared.

Then, 50.0% by weight of the cyan pigment dispersion thus prepared, glycerin 10.0% by weight, diethylene glycol 3.0% by weight, N-methylpyrrolidone 5.0% by weight, isopropyl 2.0 wt% of alcohol, 29.9 wt% of distilled water, and 0.1 wt% of allyl mustard oil as a fungicide were mixed to obtain a cyan pigment recording liquid.

Example 29 In this example, the amount of the above-mentioned distilled water was 24.9% by weight in obtaining a cyan pigment recording liquid using the cyan pigment dispersion prepared in Example 28. %, The amount of allyl mustard oil, which is a fungicide, was set to 5.1% by weight.
In the same manner as in the case of No. 8, a recording liquid of a cyan pigment was obtained.

(Example 30) In this example, the amount of the above-mentioned distilled water was 24.9% by weight in order to obtain a cyan pigment recording liquid using the cyan pigment dispersion prepared in the above-mentioned Example 28. %, The amount of glycerin is 4.6% by weight, and the amount of allyl mustard oil which is a fungicide is 10.5% by weight.
Otherwise, a recording liquid of cyan pigment was obtained in the same manner as in Example 28 described above.

(Comparative Example 6) In this comparative example, the amount of the above-mentioned distilled water was 30.0% by weight in obtaining a cyan pigment recording liquid using the cyan pigment dispersion prepared in the above-mentioned Example 28. %, While preventing addition of allyl mustard oil as an antifungal agent. Other than that, a recording liquid of cyan pigment was obtained in the same manner as in Example 28 described above.

Then, Example 15 obtained as described above was obtained.
The recording liquids of Comparative Examples 3 to 6 and Comparative Examples 3 to 6 are also similar to those of Examples 1 to 14 and Comparative Examples 1 and 2 described above.
The mold resistance and fixability were examined, and the results are shown in Table 2 below together with the content (% by weight) of allyl mustard oil in each recording liquid.

[0078]

[Table 2]

As a result, as in the case of the above-mentioned dye recording liquid, Comparative Example 3 in which no fungicide allyl mustard oil was added.
In each of the recording liquids of the pigments Nos. 6 to 6, molds were generated, while allyl mustard oil was added as an antifungal agent.
In the recording liquids of each of the 30 pigments, the generation of mold was suppressed.

Further, when the recording liquids of the respective pigments of Examples 15 to 30 were compared, Examples 1 to 1 were also compared.
Similarly to the case of the recording liquid of each dye of No. 4, when the content of allyl mustard oil is 0.1% by weight or more, no mold is generated, and when used in an ink jet recording apparatus such as an ink jet printer. In addition, clogging did not occur in the liquid flow paths and nozzles in the apparatus, and the color of each recording liquid did not change due to the action of mold.
Further, when the content of allyl mustard oil is 10% by weight or less, the fixing property of the recording liquid is less likely to be reduced, and tailing is prevented. In particular, the content of allyl mustard oil is 5% by weight or less. As a result, no tailing occurred and good fixability was exhibited. As a result, it was found that the content of allyl mustard oil in the recording liquid was preferably in the range of 0.1 to 10% by weight, and more preferably in the range of 0.1 to 5% by weight.

[0081]

As described in detail above, in the ink jet recording liquid according to the present invention, since the recording liquid contains allyl mustard oil as a water-soluble or water-dispersible fungicide, it has been conventionally used in general. As in the case of using a fungicide that has been used, the toxicity of the recording liquid is not increased and safety problems are caused, and the performance of the recording liquid is not reduced. Suppressed, when used in an ink jet recording apparatus, stable ink jet recording can be performed without causing clogging of the liquid flow path or nozzle or changing the color of the recording liquid. .

Claims (3)

[Claims] 1. An ink jet recording liquid comprising at least a coloring material, a water-soluble or water-dispersible fungicide, and water, wherein the ink further comprises allyl mustard oil as the fungicide. Recording liquid. 2. The ink jet recording liquid according to claim 1, wherein said allyl mustard oil is contained in an amount of 0.01 to 10%.
An ink jet recording liquid characterized by being contained in the range of weight%. 3. The recording liquid for inkjet according to claim 1, wherein the allyl mustard oil is contained in an amount of 0.1 to 0.1.
An ink jet recording liquid, which is contained in an amount of 5% by weight.