JP2011183770A - Coating liquid for inkjet printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating liquid for inkjet printing which excels in stability, fixity and in wear resistance especially for textiles. <P>SOLUTION: The coating liquid for inkjet printing includes water, fine polymer particle of which glass transition temperature is 0°C or less and at the same time of which acid value is 100 mgKOH/g or less, and fluororesin particle of which mean particle size is 400 nm or less, wherein the mean particle size of the fluororesin particle is two times or more of the mean particle size of the fine polymer particle. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a coating liquid for ink jet printing which has excellent color developability, stability and fixability of an ink jet print, and is particularly excellent in abrasion resistance for textiles.

  Digital textile printing using an ink jet method is a technology that can simplify the process and cope with small lots with respect to screen textile printing, and can provide textile products with low energy and low cost. Dye inks are the mainstream as inkjet inks for textile printing, but pigment inks that can simplify pre-treatment of fabrics, heating after printing, and post-treatments make the features of digital textile printing by the ink jet system more prominent.

  However, the pigment ink tends to have low abrasion resistance due to the property of realizing high color developability due to the pigment particles remaining in the vicinity of the surface of the printing medium. In particular, in textile printing applications, high abrasion resistance that suppresses color fading and color transfer due to sliding of the printing unit is required. In addition, there are also problems of so-called fastness to washing such as color fading of the printed part due to washing and dry cleaning, and contamination of the cleaning liquid with the separated color material. These performances can be apparently improved by reducing the pigment concentration in the ink, but they lead to a phenomenon in which the color development of the printing portion is lowered. In other words, in inkjet pigment inks for textile printing, there is a big problem of compatibility between printing quality represented by color development, rubbing resistance and washing fastness.

  In order to solve such a problem, a prefabricated fabric (see Patent Document 1), a binder (Patent Document 2), and a reaction between a resin emulsion in ink and a reaction liquid are used. (See Patent Document 3).

Special table 2008-504465 gazette JP 2007-126635 A JP-A-9-207424

However, a method for treating fabric and a method using a reaction solution for improving abrasion resistance and washing fastness tends to cause complexity of the apparatus and process and associated cost increase, low energy and low cost. It was difficult to fully demonstrate the features of inkjet printing with the aim of achieving the above. In addition, when trying to cope with the above performance improvement depending on the characteristics of the ink, phenomena such as an increase in the viscosity of the ink, an unstable ejection of the ink from the head, and a decrease in the stability during long-term storage of the ink appear. Sometimes it became easier to do. Furthermore, in order to ensure sufficient abrasion resistance and washing fastness, it has been difficult to ensure print quality including color development required in textile printing applications.
The present invention solves such a problem, and the object of the present invention is not to deteriorate the print quality of the ink jet ink, but particularly to the ink jet ink for textiles, the rubbing resistance, washing fastness, and storage stability. It is another object of the present invention to provide an ink-jet coating liquid that has improved discharge stability from an ink-jet head.

  The coating liquid for inkjet printing of the present invention comprises water, polymer fine particles having a glass transition temperature of 0 ° C. or lower and an acid value of 100 mgKOH / g or lower, and fluororesin particles having an average particle diameter of 400 nm or lower. In addition, the average particle size of the fluororesin particles is at least twice the average particle size of the polymer fine particles.

  The present invention does not deteriorate the print quality of the ink jet ink as an ink jet coating liquid, and particularly improves the abrasion resistance, washing fastness, and storage stability of the ink jet print for fabrics. In view of the demand for characteristics such as excellent discharge stability, the result of intensive studies has been completed.

  The coating liquid for ink jet printing according to the present invention does not contain a colorant, has water, polymer fine particles having a glass transition temperature of 0 ° C. or less, and an acid value of 100 mgKOH / g or less, and an average particle diameter of 400 nm or less. And an average particle size of the fluororesin particles is at least twice the average particle size of the polymer fine particles.

  The average particle diameter of the fluororesin particles contained in the coating liquid of the present invention is 400 nm or less, and is twice or more the average particle diameter of the polymer fine particles. The average particle diameter of the fluororesin particles and polymer fine particles is measured by a light scattering method. By controlling the average particle diameter of the fluororesin particles by the light scattering method to 400 nm or less, the sedimentation of the fluororesin particles and the stability of ejection from the inkjet head are ensured. In addition, by setting the average particle size of the fluororesin particles to at least twice the average particle size of the polymer fine particles, the abrasion resistance when the printed material is coated is improved.

The glass transition temperature of the polymer fine particles used in the coating liquid of the present invention is 0 ° C. or lower. In particular, the pigment fixing property is improved by coating the printing portion of the textile pigment ink. When the temperature exceeds 0 ° C., the fixability of the pigment gradually decreases. Preferably it is -5 degrees C or less, More preferably, it is -10 degrees C or less. Furthermore, the acid value of the polymer fine particles is 100 mgKOH / g or less. When the acid value exceeds 100 mgKOH / g, the washing fastness and wet rub resistance of the printed matter when the cloth is coated for textile use are lowered. Preferably it is 50 mgKOH / g or less, More preferably, it is 30 mgKOH / g or less.
Further, the content of the fluororesin particles in the coating liquid of the present invention is preferably in the range of 0.1% by weight to 10% by weight. When the amount of the fluororesin particles added to the coating liquid is 0.1% by weight or more, a sufficient effect of improving the abrasion resistance is obtained, and by setting the amount to 10% by weight or less, the ejection stability from the ink jet head is ensured. . Further, the content of the fluororesin particles is in the range of 10% by weight to 150% by weight with respect to the content of the polymer fine particles. By setting the content of the fluororesin particles to 10% by weight or more and 150% by weight or less with respect to the content of the polymer fine particles, it is possible to effectively improve the abrasion resistance of the printed matter.

  Examples of the fluororesin particles used in the present invention include polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene. Examples thereof include fluoroethylene copolymers, tetrafluoroethylene-perfluorodioxole copolymers, and polyvinyl fluoride. In particular, it is preferable to use polytetrafluoroethylene from the viewpoint of abrasion resistance and dispersibility.

  The coating liquid of the present invention is preferably applied to a material to be coated by ejection from an inkjet head. By discharging and coating in the same manner as the ink jet ink, a coating process is not required. Furthermore, it becomes possible to apply the coating only to a portion that requires the coating film, and the consumption of the coating liquid is reduced.

  Moreover, it is preferable to use 1,2-alkylene glycol for the coating liquid of this invention. By using 1,2-alkylene glycol, bleeding is reduced and print quality is improved. Examples of 1,2-alkylene glycols used in the present invention are 1, 5 or 6 carbon atoms such as 1,2-hexanediol, 1,2-pentanediol and 4-methyl-1,2-pentanediol, 2-alkylene glycol is preferred. Among them, 1,6-hexanediol and 4-methyl-1,2-pentanediol having 6 carbon atoms are preferable. The amount of these 1,2-alkylene glycols added is 0.3% to 30% by weight (hereinafter sometimes simply referred to as “%”), more preferably 0.5% to 10%. It is also preferable to use glycol ether. As this glycol ether, it is preferable to use diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether. The addition amount of these glycol ethers is 0.1% to 20%, more preferably 0.5% to 10%.

  Furthermore, the coating liquid of the present invention preferably uses an acetylene glycol surfactant and / or an acetylene alcohol surfactant. By using an acetylene glycol surfactant and / or an acetylene alcohol surfactant, bleeding is further reduced and printing quality is improved. The acetylene glycol surfactant and / or acetylene alcohol surfactant used in the present invention is 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetra. From alkylene oxide adducts of methyl-5-decyn-4,7-diol, 2,4-dimethyl-5-decyn-4-ol and alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol One or more selected are preferred. These acetylene glycol surfactants and / or acetylene alcohol surfactants are available as Air Products (UK) Olfin 104 series, Nissin Chemical Industry Olfin E1010 and other E series, Surfynol 465 or Surfinol 61, etc. It is available. Addition of these improves the drying property of printing, and enables high-speed printing.

  Further, by using two or more selected from the group consisting of the aforementioned 1,2-alkylene glycols, acetylene glycol surfactants and / or acetylene alcohol surfactants, and glycol ethers, blurring is further reduced. Can be made. For example, a combination of 1,2-alkylene glycol and an acetylene glycol surfactant and / or acetylene alcohol surfactant, a combination of a glycol ether and an acetylene glycol surfactant and / or an acetylene alcohol surfactant Is mentioned.

  On the other hand, the coating liquid of the present invention has a humectant, a solubilizing agent, a penetration control agent, a viscosity adjuster for the purpose of ensuring its standing stability, stable ejection from an inkjet head, improvement of clogging, or prevention of ink deterioration, etc. Various additives such as an agent, a pH adjuster, a solubilizing agent, an antioxidant, an antiseptic, an antifungal agent, a corrosion inhibitor, and a chelate for capturing metal ions that affect the dispersion can also be added.

  Hereinafter, the present invention will be described more specifically. The present invention is not limited to the following examples.

Example 1
(1) Production of Black Ink for Inkjet Printing Mix 100.0 parts by weight of commercially available carbon black (# 44: manufactured by Mitsubishi Chemical Corporation) with 900.0 parts by weight of water, and use Eiger Motor Mill M250 (manufactured by Eiger Japan). The dispersion was performed for 2 hours under the conditions of a bead filling rate of 70% and a rotational speed of 5000 rpm. To this dispersion, 1500.0 parts by weight of sodium hypochlorite (effective chlorine concentration: 12%) was added dropwise and reacted for 5 hours while stirring with an Eiger motor mill, then the temperature was controlled at 100 ° C. and stirred for 8 hours. . Subsequently, the obtained slurry was filtered, washed with water, and adjusted to a carbon black pigment concentration of 15% by weight to obtain a surface-treated carbon black dispersion.

  Next, 33.3 parts by weight of the carbon black dispersion, 2.0 parts by weight of 1,2-hexanediol, 1.5 parts by weight of butyltriglycol, and 0.3 parts by weight of Surfynol 104 (manufactured by Nissin Chemical) Surfynol 465 (manufactured by Nissin Chemical Co., Ltd.) 0.5 parts by weight, 10.0 parts by weight of glycerol, 3.0 parts by weight of trimethylolpropane, 4.0 parts by weight of triethylene glycol, 1.0 part by weight of triethanolamine Then, 44.4 parts by weight of ion-exchanged water was mixed in a container equipped with stirring means. Then, it filtered with a 10 micrometer membrane filter, and was set as the black ink for inkjet printing whose black pigment density | concentration is 5 weight%.

(2) Preparation of polymer fine particle dispersion 1 A reaction vessel is equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, and 100 parts by weight of ion-exchanged water is added and stirred at 70 ° C. in a nitrogen atmosphere at a polymerization initiator In addition, 0.2 parts by weight of potassium persulfate was added in advance, and each monomer total of 100 parts by weight of styrene, 69.5 parts by weight of ethyl acrylate, 12.5 parts by weight of butyl acrylate, and 2.0 parts by weight of methacrylic acid. A monomer solution containing 7 parts by weight of ion-exchanged water, 0.05 parts by weight of sodium lauryl sulfate, and 0.02 parts by weight of t-dodecyl mercaptan is added dropwise to 40% by weight of the parts by weight at 70 ° C. for reaction. To produce the primary material. To the primary material, 2 parts by weight of a 10% by weight ammonium persulfate solution was added and stirred. Further, 30 parts by weight of ion exchange water, 0.2 parts by weight of potassium lauryl sulfate, the remaining 60% by weight of the monomer, t- A reaction solution consisting of 0.5 parts by weight of dodecyl mercaptan was added with stirring at 70 ° C. to cause a polymerization reaction, and then neutralized with sodium hydroxide to a pH of 8 to 8.5. Then, it filtered with a 0.3 micrometer filter, the resin solid content concentration was adjusted to 40 weight%, and the polymer fine particle water dispersion 1 was obtained. A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature (hereinafter referred to as “Tg”) was measured with a differential operation calorimeter (EXSTAR 6000DSC manufactured by Seiko Denshi). It was. The particle diameter was measured using a Microtrac particle size distribution analyzer UPA250 (manufactured by Nikkiso), and it was 130 nm.

The acid value was measured by the following method. The polymer fine particle aqueous dispersion 1 is collected in a state before neutralization with sodium hydroxide, and the solid content concentration is accurately measured by a thermobalance (TG-2121 manufactured by Seiko Denshi Kogyo). Next, about 10 g of this polymer fine particle aqueous dispersion is accurately weighed, put into a stoppered Erlenmeyer flask, and 100 ml of 2-propanol-tetrahydrofuran mixture (1: 2) is added and dissolved. As an indicator, and titrating with a 0.1 mol / L 2-propanol potassium hydroxide solution until a pale red color lasting 30 seconds is obtained. The acid value is determined by the formula (1).
Acid value (mgKOH / g) = (5.611 × a × f) / S (1)
S: Sample collection amount (g)
a: Consumption of 0.1 mol / L 2-propanol potassium hydroxide solution (ml)
f: Factor of 0.1 mol / L 2-propanol potassium hydroxide solution where a is the titration value (ml) -blank value (ml)
The acid value of the polymer fine particle dispersion 1 determined by the above method was 20 mgKOH / g.

(3) Preparation of fluororesin particle dispersion 1 As the fluororesin particles, polytetrafluoroethylene (hereinafter referred to as [PTFE]) powder (KTL-500F manufactured by Kitamura Co., Ltd.) was used. 40 parts by weight of KTL-500F, 80 parts by weight of ion-exchanged water, and 10 parts by weight of Olfine E1010 (Nisshin Chemical Industry Co., Ltd.) were mixed. Then, it disperse | distributed over 2 hours using the Eiger mill using a zirconia bead. Subsequently, it moved to another container, 30 weight part of ion-exchange water was added, and also it stirred for 1 hour. And after removing a zirconia bead, it filtered with a 10 micrometer membrane filter, adjusted with ion-exchange water, and was set as the fluororesin particle dispersion liquid 1 whose PTFE density | concentration is 25 weight%.

  The average particle diameter of the fluororesin particles and the ratio of the average particle diameter of the fluororesin particles to the average particle diameter of the polymer fine particles are shown in Tables 1 and 3. The same applies to the following examples and comparative examples.

(4) Preparation of coating liquid for inkjet printing Table 2 shows examples of compositions suitable for coating liquid for inkjet printing. The coating liquid for inkjet printing of the present invention was prepared by mixing the polymer fine particle dispersion 1 and the fluororesin particle dispersion 1 prepared by the above method and mixing with the vehicle components shown in Table 2. In addition, 0.05% by weight of the top side 240 (manufactured by Permachem Asia Co., Ltd.) is used to prevent corrosion of the coating liquid in the remaining amount of water in the examples and comparative examples of the present invention, in order to prevent corrosion of the inkjet head member. In order to reduce the influence of 0.02% by weight of benzotriazole and metal ions in the coating solution, 0.04% by weight of EDTA (ethylenediaminetetraacetic acid) · 2Na salt was added to ion-exchanged water.

(5) Abrasion resistance test and dry cleaning property test For the preparation of the test sample, Seiko Epson Corporation PX-A650 was used as an inkjet printer, using the black ink for inkjet printing and the coating liquid for inkjet printing. . The test sample was obtained by printing black ink and the coating liquid on the entire surface of a cotton cloth, and the printing order of the ink and the coating liquid was that the coating liquid was printed and applied after printing the ink. The sample was subjected to friction fastness by rubbing 100 times with a load of 200 g using a Gakushin type friction fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd. Evaluation was made at two levels, dry and wet, in accordance with JIS L0849, a Japanese Industrial Standard (JIS) that confirms the degree of ink peeling. Similarly, the dry cleaning test was evaluated by the method B of JIS L0860. Table 1 shows the results of the abrasion resistance test and the dry cleaning test.

(6) Test of ejection stability Using the above-described coating liquid for inkjet printing, using PX-A650 manufactured by Seiko Epson Corporation as an inkjet printer, Microsoft Word on XeroxP paper A4 size manufactured by Fuji Xerox Co., Ltd. at 35 ° C. and 35% atmosphere. Evaluation was performed by printing 100 pages at a rate of 4000 characters / page with a standard of character size 11 and MSP Gothic. AA when there is no printing disorder at all, A when there is printing disorder at A, B at 2 to 3 printing disorder B, C at 4 to 5 printing disorder, 6 or more printing disorder The results are shown in Table 1 as D.

(Example 2)
Example 2 is the same as Example 1 except that the polymer fine particle dispersion used in Example 1 is a commercially available acrylic resin emulsion (Tg-20 ° C., acid value 20 mgKOH / g, average particle size 100 nm). A coating liquid for inkjet printing was prepared using the fluororesin particle dispersion liquid 1. The acrylic resin emulsion used here was designated as polymer fine particle dispersion 2. The coating liquid composition table is shown in Table 2.

  Next, evaluation was performed together with the black ink for inkjet printing in the same manner as in Example 1. Table 1 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

(Comparative Example 1)
In Comparative Example 1, the Tg of the polymer fine particles is at a level exceeding 0 ° C.
Comparative Example 1 was the same as in Example 1 except that the polymer fine particle dispersion used was a commercially available acrylic resin emulsion (Tg 10 ° C., acid value 20 mg KOH / g, average particle size 100 nm). A coating liquid for ink jet printing was prepared using the particle dispersion 1. The acrylic resin emulsion used here was a polymer fine particle dispersion 3. The coating liquid composition table is shown in Table 2.

  Next, evaluation was performed together with the black ink for inkjet printing in the same manner as in Example 1. Table 1 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

(Comparative Example 2)
In Comparative Example 2, the Tg of the polymer fine particles is at a level exceeding 0 ° C.
Comparative Example 2 was the same as in Example 1 except that the polymer fine particle dispersion used was a commercially available acrylic resin emulsion (Tg 30 ° C., acid value 20 mgKOH / g, average particle size 100 nm). A coating liquid for ink jet printing was prepared using the particle dispersion 1. The acrylic resin emulsion used here was a polymer fine particle dispersion 4. The coating liquid composition table is shown in Table 2.

  Next, evaluation was performed together with the black ink for inkjet printing in the same manner as in Example 1. Table 1 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

(Comparative Example 3)
In Comparative Example 3, the acid value of the polymer fine particles is at a level exceeding 100 mgKOH / g.
Comparative Example 3 is the same as Example 1 except that the polymer fine particle dispersion used in Example 1 was a commercially available acrylic resin emulsion (Tg-5 ° C., acid value 130 mgKOH / g, average particle size 150 nm). A coating liquid for inkjet printing was prepared using the fluororesin particle dispersion liquid 1. The acrylic resin emulsion used here was a polymer fine particle dispersion 5. The coating liquid composition table is shown in Table 2.

  Next, evaluation was performed together with the black ink for inkjet printing in the same manner as in Example 1. Table 1 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

(Comparative Example 4)
In Comparative Example 4, the average particle diameter of the fluororesin particles is at a level exceeding 400 nm.
In Comparative Example 4, a coating liquid for inkjet printing was prepared using the polymer fine particle dispersion 2 in the same manner as in Example 2, except that the average particle diameter of the fluororesin particles used was 0.5 μm. did. The fluororesin particle dispersion used here was designated as fluororesin particle dispersion 2. The coating liquid composition table is shown in Table 2.

  Next, evaluation was performed together with the black ink for inkjet printing in the same manner as in Example 1. Table 1 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

(Comparative Example 5)
In Comparative Example 5, the average particle diameter of the fluororesin particles used is at a level that is 1.5 times the average particle diameter of the polymer fine particles.
Comparative Example 5 was the same as Example 1 except that the polymer fine particle dispersion used in Example 1 was a commercially available acrylic resin emulsion (Tg-10 ° C., acid value 20 mgKOH / g, average particle size 200 nm). A coating liquid for inkjet printing was prepared using the fluororesin particle dispersion liquid 1. The acrylic resin emulsion used here was a polymer fine particle dispersion 6. The coating liquid composition table is shown in Table 2.

  Next, evaluation was performed together with the black ink for inkjet printing in the same manner as in Example 1. Table 1 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

(Comparative Example 6)
In Comparative Example 6, the average particle diameter of the fluororesin particles used is at a level that is approximately the same as the average particle diameter of the polymer fine particles.
Comparative Example 6 was the same as Example 1 except that the polymer fine particle dispersion used in Example 1 was a commercially available acrylic resin emulsion (Tg-10 ° C., acid value 20 mgKOH / g, average particle size 300 nm). A coating liquid for inkjet printing was prepared using the fluororesin particle dispersion liquid 1. The acrylic resin emulsion used here was a polymer fine particle dispersion 7. The coating liquid composition table is shown in Table 2.

  Next, evaluation was performed together with the black ink for inkjet printing in the same manner as in Example 1. Table 1 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

(Example 3)
(1) Production of magenta ink for inkjet printing Pigment violet 19 (quinacridone pigment: manufactured by Clariant) was used as magenta ink. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 45 parts by weight of styrene, 30 parts by weight of polyethylene glycol 400 acrylate, 10 parts by weight of benzyl acrylate, 2.0 parts by weight of acrylic acid, t- Add 0.3 parts by weight of dodecyl mercaptan and heat to 70 ° C., separately prepared 150 parts by weight of styrene, 100 parts by weight of polyethylene glycol 400 acrylate, 15 parts by weight of acrylic acid, 5.0 parts by weight of butyl acrylate, t-dodecyl mercaptan 1.0 part by weight, 20 parts by weight of methyl ethyl ketone and 1.0 part by weight of sodium persulfate were placed in a dropping funnel, and the dispersion polymer was subjected to a polymerization reaction while dropping into a reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40% by weight.

  Subsequently, 40 parts by weight of the dispersion polymer solution, 30 parts by weight of Pigment Violet 19 (quinacridone pigment: Clariant), 100 parts by weight of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts by weight of methyl ethyl ketone were mixed. Then, using an ultra-high pressure homogenizer (Ultimizer HJP-25005 manufactured by Sugino Machine Co., Ltd.), it was dispersed by passing 15 passes at 200 MPa. Then, it moved to another container, 300 weight part of ion-exchange water was added, and also it stirred for 1 hour. And the whole amount of methyl ethyl ketone and a part of water were distilled off using the rotary evaporator, and it neutralized with 0.1 mol / L sodium hydroxide, and adjusted to pH9. Then, it filtered with a 0.3 micrometer membrane filter and adjusted with ion-exchange water, and obtained the magenta pigment dispersion whose pigment concentration is 15 weight%.

  Next, 26.7 parts by weight of the magenta pigment dispersion, 3.0 parts by weight of 1,2-hexanediol, 1.0 part by weight of butyltriglycol, and 0.3 parts by weight of Surfynol 104 (manufactured by Nisshin Chemical Co., Ltd.) , Surfinol 465 (manufactured by Nissin Chemical Co., Ltd.) 0.5 parts by weight, 16.0 parts by weight of glycerol, 3.0 parts by weight of trimethylolpropane, 4.0 parts by weight of triethylene glycol, 1.0 part by weight of triethanolamine Then, 44.5 parts by weight of ion-exchanged water was mixed in a container equipped with stirring means. Thereafter, the mixture was filtered through a 10 μm membrane filter to obtain a magenta ink for inkjet printing having a magenta pigment concentration of 4% by weight.

(2) Preparation of Polymer Fine Particle Dispersion 2 A commercially available aqueous urethane resin dispersion (Tg-15 ° C., acid value 20 mgKOH / g, average particle size 120 nm) was used as the polymer fine particle dispersion. This aqueous urethane resin dispersion was designated as polymer fine particle dispersion 8.

(3) Preparation of Fluororesin Particle Dispersion 1 Fluororesin particles 1 were prepared and used in the same manner as in Example 1.

(4) Preparation of coating liquid for inkjet printing Table 4 shows examples of compositions suitable for coating liquid for inkjet printing. The coating liquid for inkjet printing of the present invention is prepared by mixing the polymer fine particle dispersion 8 and the fluororesin particle dispersion 1 prepared in the same manner as in Example 1 and mixing with the vehicle components shown in Table 4. Produced. It should be noted that the remaining amount of water in the examples and comparative examples of the present invention is 0.05% of the top side 240 (manufactured by Permachem Asia) for preventing the coating liquid from being corroded, and benzoin for preventing the corrosion of the ink jet head member. 0.02% of triazole and 0.04% of EDTA (ethylenediaminetetraacetic acid) · 2Na salt were added to ion-exchanged water in order to reduce the influence of metal ions in the coating solution.

(5) Abrasion resistance test and dry cleaning property test For the preparation of the test sample, the magenta ink for inkjet printing and the coating liquid for inkjet printing were used, and PX-A650 manufactured by Seiko Epson Corporation was used as an inkjet printer. . The test sample was obtained by printing a magenta ink and the coating liquid on the entire surface of a cotton cloth, and the printing order of the ink and the coating liquid was to print and apply the coating liquid after printing the ink. The sample was subjected to friction fastness by rubbing 100 times with a load of 200 g using a Gakushin type friction fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd. The test was evaluated in the same manner as in Example 1. The test results are shown in Table 3.

(6) Test of ejection stability Evaluation was performed in the same manner as in Example 1 using the coating liquid for inkjet printing. The test results are shown in Table 3.

Example 4
(1) Preparation of cyan ink for inkjet printing Pigment Blue 15: 3 was used as the cyan ink. Example 4 was prepared in the same manner as in Example 3 except that Pigment Violet 19 used in Example 3 was replaced with Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant), and the pigment concentration was 15% by weight. A cyan pigment dispersion was obtained.

  Next, 26.7 parts by weight of the cyan pigment dispersion, 3.0 parts by weight of 1,2-hexanediol, 1.0 part by weight of butyltriglycol, and 0.3 parts by weight of Surfynol 104 (manufactured by Nissin Chemical) Surfynol 465 (manufactured by Nissin Chemical Co., Ltd.) 0.5 parts by weight, 17.0 parts by weight of glycerin, 3.0 parts by weight of trimethylolpropane, 5.0 parts by weight of triethylene glycol, 1.0 part by weight of triethanolamine Then, 42.5 parts by weight of ion-exchanged water was mixed in a container equipped with stirring means. Thereafter, the mixture was filtered through a 10 μm membrane filter to obtain a cyan ink for inkjet printing having a cyan pigment concentration of 4% by weight.

(2) Preparation of Polymer Fine Particle Dispersion 2 Polymer fine particle dispersion 8 used polymer fine particle dispersion 8 as in Example 3.

(3) Preparation of fluororesin particle dispersion 1 Fluorine resin particles 1 were prepared and used in the same manner as in Example 3.

(4) Preparation of coating liquid for ink jet printing The same coating liquid for ink jet printing as in Example 3 was used.
(5) Abrasion resistance test and dry cleaning test

  For the preparation of the test sample, the cyan ink for inkjet printing and the coating liquid for inkjet printing were used, and PX-A650 manufactured by Seiko Epson Corporation was used as an inkjet printer. The test sample was obtained by printing the entire surface of the cyan ink and the coating liquid on a cotton cloth, and the printing order of the ink and the coating liquid was that the coating liquid was printed and applied after the ink was printed. The sample was subjected to friction fastness by rubbing 100 times with a load of 200 g using a Gakushin type friction fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd. The test was evaluated in the same manner as in Example 1. The test results are shown in Table 3.

(6) Test of ejection stability Evaluation was performed in the same manner as in Example 1 using the coating liquid for inkjet printing. The test results are shown in Table 3.

(Reference Example 1)
In Reference Example 1, the blending amount of the fluororesin particles into the coating liquid is at a level exceeding 10% by weight.
Reference Example 1 is the same as in Example 3, except that the blending amount of the fluororesin particle dispersion 1 in the coating liquid for inkjet printing was 15% by weight in terms of solid content. Prepared. Table 4 shows the coating liquid composition table.

  Next, evaluation was performed together with magenta ink for inkjet printing in the same manner as in Example 3. Table 3 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

(Comparative Example 8)
Comparative Example 8 is a level using a coating liquid that does not contain fluororesin particles and polymer fine particles.
In Comparative Example 8, a coating liquid for inkjet printing was prepared in the same manner as in Example 4 except that the fluororesin particle dispersion and the polymer fine particle dispersion in the coating liquid for inkjet printing were not added. Table 4 shows the coating liquid composition table.

  Next, the ink was evaluated together with the cyan ink for inkjet printing in the same manner as in Example 4. Table 3 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

(Comparative Example 9)
Comparative Example 9 is a level using a coating solution that does not contain polymer fine particles.
In Comparative Example 9, a coating liquid for inkjet printing was prepared in the same manner as in Example 4 except that the polymer fine particle dispersion in the coating liquid for inkjet printing was not added. Table 4 shows the coating liquid composition table.

  Next, the ink was evaluated together with the cyan ink for inkjet printing in the same manner as in Example 4. Table 3 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

(Comparative Example 10)
Comparative Example 10 is a level using a coating liquid that does not contain fluororesin particles.
In Comparative Example 10, a coating liquid for inkjet printing was prepared in the same manner as in Example 4, except that the fluororesin particle dispersion in the coating liquid for inkjet printing was not added. Table 4 shows the coating liquid composition table.

  Next, the ink was evaluated together with the cyan ink for inkjet printing in the same manner as in Example 4. Table 3 shows the results of the abrasion resistance test, the dry cleaning property test, and the ejection stability test.

Claims (5)

  It contains no colorant, water, polymer fine particles having a glass transition temperature of 0 ° C. or less and an acid value of 100 mgKOH / g or less, and fluororesin particles having an average particle size of 400 nm or less, A coating liquid for inkjet printing, wherein the average particle diameter of the fluororesin particles is at least twice the average particle diameter of the polymer fine particles.   The content of the fluororesin particles is 0.1% to 10% by weight, and the content of the fluororesin particles is in the range of 10% to 150% by weight with respect to the content of the polymer fine particles. The coating liquid for ink jet printing according to claim 1.   The coating liquid for inkjet printing according to claim 1, wherein the fluororesin particles are polytetrafluoroethylene.   The coating liquid for inkjet printing according to any one of claims 1 to 3, wherein the coating liquid is used for fabrics.   The coating liquid for inkjet printing according to any one of claims 1 to 4, wherein the coating liquid is applied to the fabrics by discharging from an inkjet head.