JP2010162726A - Ink set of inkjet for cloth and inkjet dyeing prevention method using the ink set - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set of inkjet for fabric, which suppresses the generation of bleeding even to fabric which is not subjected to preparatory treatment for an inkjet and is excellent in injection stability and an inkjet dyeing prevention method using the ink set. <P>SOLUTION: In the inkjet dyeing prevention method, the ink set of inkjet for a fabric is used which is composed of a first ink containing water, a liquid moisturizer, and a water soluble high molecular compound and a second ink containing water, fine resin particles, and a water soluble organic solvent. After the first ink and the second ink are applied to a fabric, a coloring agent is applied to make printed articles. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an inkjet dye-resisting method. More specifically, the present invention relates to an ink-jet ink set for fabrics that suppresses bleeding even on a fabric that has not been subjected to inkjet pretreatment, and has excellent light-emitting properties, and ink-jet dyeing using the same. It is about the method.

  A method for inhibiting dye fixation by adding a wax to the dyeing paste is known in the dyeing prevention field, as described in, for example, dyeing and finishing technology, Kazuo Shiozawa, Jinshoshokan, etc. Is the method. However, when an aqueous ink containing wax is directly ejected onto a cloth that is not subjected to inkjet pretreatment, an image is formed on the cloth. For this reason, the inkjet pre-processing which usually provided the component which consists of water-soluble high molecular compounds, such as carboxymethylcellulose and sodium alginate, to the fabric has been performed (for example, refer patent document 1). In this method, it is considered that the water-soluble polymer compound in the fabric has acted as an ink holding component (absorbing layer) to prevent bleeding.

  Unlike the ink jet printing process that can be handled on demand, such a pretreatment for ink jet of a fabric needs to be processed in a certain amount in advance. Therefore, it takes a lot of time and the pretreatment cloth Since it has inventory and processing cost, it has become a big obstacle in spreading inkjet printing more.

  In addition, as described above, by applying a paste to the fabric, it is easy to stay on the fabric surface due to the mechanism that suppresses bleeding by absorbing the ink. There is also a problem of not being dyed.

  As an attempt to eliminate pretreatment by applying a functional liquid for suppressing bleeding using an ink jet head, a method is disclosed in which an image is trimmed with a first ink containing a bleeding inhibitor (for example, a patent). Reference 2). In the method described in Patent Document 2, addition of a compound having a property of repelling water with a hydrophobic substance is disclosed as a bleed inhibitor, but it is possible to prevent bleed at the boundary between a white background and an image portion or to have a different specific hue. It is considered that the invention is limited to the prevention of blurring of the boundary. The method described in Patent Document 2 has a problem that it cannot cope with the suppression of blurring in a printed image having a gradation expression with increased expressive power. Also, it is not suitable for fine line and detail image expression. This is because the print area of the first ink and the print image of the second ink must be accurately matched, but the fabric is easily stretchable and the printing position is very difficult to align. Furthermore, since the first ink itself also bleeds into the fabric, very fine fine lines cannot be drawn in principle.

JP-A-6-116880 JP-A-9-296380

  SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and its object is to suppress the occurrence of bleeding even on a fabric that has not been subjected to inkjet pretreatment, and the inkjet ink for fabric that has excellent emission stability. It is to provide a set and an inkjet dye-resisting method using the set.

  The above object of the present invention is achieved by the following configurations.

  1. An inkjet ink set for fabric, comprising: a first ink containing water, a liquid humectant, and a water-soluble polymer compound; and a second ink containing water, resin fine particles, and a water-soluble organic solvent. .

  2. The inkjet ink set for fabric according to 1, wherein the first ink contains a solid moisturizing agent.

  3. The water-soluble polymer compound is polyvinyl pyrrolidone, polyethylene glycol, ethylene oxide propylene oxide copolymer, glycerin polyethylene oxide adduct, glycerin polypropylene adduct, diglycerin polyethylene oxide adduct, and diglycerin polypropylene adduct. And the total amount of the water-soluble polymer compound is 1% by mass or more and less than 10% by mass as a solid content with respect to the total mass of the first ink. The inkjet ink set for cloth according to 1 or 2.

  4). The inkjet ink set for cloth according to any one of 1 to 3, wherein the first ink contains a water-soluble cationic polymer.

  5. An inkjet dyeing method comprising applying a colorant after applying the first ink and the second ink to a fabric using the inkjet ink set for fabric according to any one of 1 to 4 above.

  6). 6. The inkjet dyeing method according to 5 above, wherein the first ink is applied while heating the fabric.

  7). The printer used to apply the first ink and the second ink to the fabric is a printer in which the first ink head and the second ink head are arranged on the same carriage, and one scan is performed. 6. The ink-jet dyeing method as described in 5 above, wherein the first ink and the second ink are applied onto the fabric.

  8). 8. The inkjet dyeing method according to 5 or 7, wherein the first ink and the second ink are applied while heating the fabric.

  According to the present invention, there is provided an inkjet ink set for a fabric that suppresses the occurrence of bleeding and has excellent emission stability even for a fabric that has not been subjected to inkjet pretreatment, and an inkjet dyeing method using the same. I was able to.

It is a schematic diagram which shows the partial structure of the printer for evaluation used in the Example.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventors have found that a first ink containing water, a liquid humectant, and a water-soluble polymer compound, and a second ink containing water, resin fine particles, and a water-soluble organic solvent. An inkjet dye-resisting method comprising: applying a colorant after applying a first ink and a second ink to a fabric using an inkjet ink set for fabric characterized in that As a result, it has been found that an inkjet dyeing method that suppresses the occurrence of bleeding and is excellent in emission stability can be realized even for a fabric that has not been subjected to inkjet pretreatment.

  Hereinafter, the present invention will be described in more detail.

  First, the configuration of the first ink and the second ink according to the present invention will be described.

<First ink>
The first ink according to the present invention is an ink liquid containing a water-soluble polymer compound to suppress bleeding during printing using the second ink, and is applied to the fabric from the inkjet head. . The water viscosity of the water-soluble polymer compound according to the present invention increases as the solid content of the water-soluble polymer compound increases. This high viscosity characteristic is used to prevent bleeding after the second ink has landed on the fabric.

  Although a method of adding a water-soluble polymer compound to the second ink is also conceivable, a large amount of resin fine particles are added to the second ink, so that a sufficient amount of the water-soluble polymer compound can be stabilized to suppress bleeding. It has been found that it is very difficult to add to the first ink, and it has been found that adding to the first ink is a preferred embodiment, leading to the present invention.

  Hereinafter, each additive which comprises the 1st ink which concerns on this invention is demonstrated.

[Water-soluble polymer compound]
The water-soluble polymer compound added to the first ink according to the present invention is not particularly limited as long as it sufficiently suppresses the bleeding of the second ink and does not inhibit the ink jetting property of the first ink. be able to. In order not to change the texture of the printed matter, it is preferable that the water-soluble polymer compound is easy to remove in the washing step after printing and coloring.

  Examples of water-soluble polymer compounds include polyvinylpyrrolidone, polyethylene glycol, ethylene oxide propylene oxide copolymer, glycerin polyethylene oxide adduct, glycerin polypropylene adduct, diglycerin polyethylene oxide adduct, diglycerin polypropylene addition. Products, carboxymethyl cellulose, methyl cellulose, sodium alginate, polyvinyl alcohol and the like.

  Preferable water-soluble polymer compounds include polyvinylpyrrolidone, polyethylene glycol, ethylene oxide propylene oxide copolymer, glycerin polyethylene oxide adduct, glycerin polypropylene adduct, diglycerin polyethylene oxide adduct, diglycerin polypropylene. Examples include adducts.

  Since the preferable addition amount of the water-soluble polymer compound varies depending on the molecular weight and the type thereof, it is preferable to appropriately select the optimum conditions.

  Among the above water-soluble polymer compounds, polyvinyl pyrrolidone is a particularly preferable water-soluble polymer compound that can be stably ejected from an inkjet head and has a large blurring suppression effect.

  Polyvinyl pyrrolidone is classified by viscosity characteristic value correlating with the molecular weight, and K (Kollidon) 15, 30, 60 and the like can be preferably used. In particular, K15, K30 have high inkjet ejection stability and suppress bleeding. It is effective and preferable. The addition amount to the first ink is preferably in the range of 2 to 20% by mass as the solid content.

  Polyethylene glycol can also be preferably used, and polyethylene glycol having a weight average molecular weight of 600 or more can be preferably used. Furthermore, those having a weight average molecular weight of 1000 or more and 4000 or less are particularly effective because they are effective in suppressing bleeding. The amount of polyethylene glycol added to the first ink is preferably 2-20% by mass.

  Examples of the ethylene oxide / propylene oxide copolymer include those having a structure in which polyethylene oxide is added to the end of polypropylene glycol, those having a structure in which polypropylene oxide is added to the end of polyethylene glycol, and ethylene oxide-propylenoxide. A random copolymer etc. are mentioned.

  As a structure having polyethylene oxide added to the end of polypropylene glycol, ADEKA Corporation's Adeka Pluronic L, P, F series, etc., various ethylene oxide-propylene oxide blend ratio products and various molecular weight products are commercially available. And you can choose from them. Particularly, a water-soluble polypropylene glycol part having a molecular weight of 2000 or less can be preferably used. Specifically, L-62, L-64, F-68, F-88, F-108, L-44, L-34, L-23 (above, manufactured by ADEKA Corporation) can be exemplified. .

  As a structure in which polypropylene oxide is added to the end of polyethylene glycol, it can also be selected from reverse types such as ADEKA Corporation, 17R-2, 17R-3, and 17R-4.

  The amount of ethylene oxide / propylene oxide copolymer added to the first ink is preferably in the range of 2 to 20% by mass.

  As the polyethylene oxide adduct of diglycerin, it can be used by selecting from SC-E series of Sakamoto Pharmaceutical Co., Ltd., for example, SC-E450, SC-E750, SC-E1000, SC-E1500, etc. are preferably used. be able to. The addition amount to the first ink is preferably in the range of 2 to 20% by mass.

  As a polypropylene adduct of diglycerin, it can be used by selecting from SC-P series of Sakamoto Yakuhin Kogyo Co., Ltd., and SC-P400, SC-P750, SC-P1000, etc. can be preferably used. The addition amount to the first ink is preferably in the range of 2 to 20% by mass.

  With respect to the amount of the water-soluble polymer compound added to the first ink, the preferred range mentioned above is less than the lower limit, and a sufficient blur suppression effect cannot be exhibited. If the amount exceeds the upper limit, the inkjet ejection is unstable. It is not preferable.

  These water-soluble polymer compounds may be used alone or in combination of two or more.

[Liquid moisturizer]
A liquid humectant is preferably added to the first ink according to the present invention from the viewpoint of suppressing nozzle clogging of the first ink in the inkjet head. This is because the liquid humectant has a function of delaying drying of moisture and delaying precipitation of the first ink content. However, since the liquid humectant has the property of easily causing the second ink to bleed at the same time, it is easy to determine the type and amount of addition from the viewpoint of both the head clogging prevention effect and the bleed generation. is there.

  Examples of the liquid humectant applicable to the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin and the like.

  The amount of liquid humectant added to the first ink is preferably selected within the range of 5% by mass or more and less than 40% by mass.

[Solid moisturizer]
It is preferable to add a solid humectant to the first ink according to the present invention. The solid humectant, like the liquid humectant, has the effect of preventing the precipitation of each additive due to drying and increasing the color density. In particular, the combined use with a liquid humectant is preferable from the viewpoint of improving both the drying prevention effect and the effect of increasing the color density.

  Examples of the solid humectant include water-soluble amides, sulfonamides, urea, urea derivatives and the like, and urea is particularly preferable.

  The solid humectant is preferably used in the first ink in an amount ranging from 2% by mass to less than 15% by mass.

(Water-soluble cationic polymer)
A water-soluble cationic polymer can be added to the first ink according to the present invention. The water-soluble cationic polymer is effective in preventing bleeding of the colorant when a colorant is added to the second ink.

  As the cationic polymer that can be used in the present invention, those that lower the solubility and dispersibility of the colorant by ionic bonding with the colorant and the dispersant in the second ink can be used. By using such a water-soluble cationic polymer, it is possible to prevent bleeding of the colorant by causing aggregation of the colorant and its dispersant after the landing of the second ink. Addition of a compound that suppresses bleeding by a mechanism different from that of the water-soluble polymer compound or resin fine particles, such as a water-soluble cationic polymer, is a preferable embodiment for suppressing bleeding.

  As the water-soluble cationic polymer, for example, polyallylamine, polydiallylamine, polymethyldiallylamine, polydiallyldimethylammonium chloride and the like can be used. Specific examples thereof include PAA-D41-HCl, PAS-21Cl, PAS-M-1L, PAS-H-1L, PAS-J-81L, etc. sold by Nittobo.

  The physical properties of the first ink can be adjusted according to the fabric. The viscosity is preferably 3 mPa · s or more and less than 20 mPa · s. The surface tension is preferably 25 mN / m or more and 70 mN / m or less.

  When the first ink is unevenly distributed on the fabric surface and it is desired to enhance the reaction on the surface, the viscosity is preferably 5 mPa · s or more and less than 20 mPa · s, and the surface tension is preferably 35 mN / m or more and less than 70 mN / m.

  When it is desired to penetrate the first ink to the deep part of the fabric, the viscosity is preferably 3 mPa · s or more and less than 12 mPa · s, and the surface tension is preferably 20 mN / m or more and less than 35 mN / m.

  In order to adjust the surface tension and the viscosity, various water-soluble organic solvents can be added. For example, alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol) , Dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine) , Morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethyl Tetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocycles (eg, 2 -Pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (for example, dimethyl sulfoxide) and the like.

  In particular, when it is desired to cause the second ink to penetrate to the deep part of the fabric to develop a color, it is preferable to use the following low surface tension solvent (in the parentheses, the surface tension of the solvent (mN / m)).

  Examples of the glycol ether include ethylene glycol monoethyl ether (28.2), ethylene glycol monobutyl ether (27.4), diethylene glycol monoethyl ether (31.8), diethylene glycol monobutyl ether (33.6), and triethylene glycol. Examples thereof include monobutyl ether (32.1), propylene glycol monopropyl ether (25.9), dipropylene glycol monomethyl ether (28.8), tripropylene glycol monomethyl ether (30.0) and the like.

  Examples of the 1,2-alkanediol include 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol (28.1), 1,2-heptanediol, and the like.

(Surfactant)
In addition, when it is desired to cause the second ink to penetrate to the deep part of the fabric to develop a color, the following surfactant can be used.

  In the first ink according to the present invention, various surfactants can be used when it is desired to penetrate the resin fine particles of the second ink deeper into the fabric. The surfactant that can be used in the present invention is not particularly limited, and examples thereof include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl ethers. Nonionic surfactants such as oxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. In particular, an anionic surfactant and a nonionic surfactant can be preferably used.

  In order to further infiltrate the colorant of the second ink into the deep part of the fabric, it is preferable to control the surface tension of the first ink to 20 mN / m or more and 35 mN / m or less, particularly a silicone-based surfactant or a fluorine-based interface. It is preferable to control the surface tension by adding an activator.

<Silicone-based surfactant or fluorine-based surfactant>
The silicone-based surfactant is preferably a polyether-modified polysiloxane compound, and examples thereof include KF-351A and KF-642 manufactured by Shin-Etsu Chemical Co., and BYK345, BYK347, and BYK348 manufactured by Big Chemie.

  The fluorine-based surfactant means a compound in which a part or all of the fluorine-based surfactant is substituted with a fluorine atom instead of the hydrogen atom bonded to the carbon of the hydrophobic group of the normal surfactant. Of these, those having a perfluoroalkyl group in the molecule are preferred.

  Among the fluorosurfactants, a certain kind is a product name of Megafac F from Dainippon Ink and Chemicals, and a product name of Surflon from Asahi Glass Co., Minnesota Mining and・ Manufacturing Company under the product name Fluorad FC, Imperial Chemical Industry under the name Monfloor, and EI Dupont Nemeras & Company Zonyls And the product name Licobet VPF from the company Farbeberke Hoechst.

  Examples of nonionic fluorosurfactants include Megafax 144D manufactured by Dainippon Ink and Surflon S-141 and 145 manufactured by Asahi Glass Co., and amphoteric fluorosurfactants. Examples of the agent include Surflon S-131 and 132 manufactured by Asahi Glass Co., Ltd.

<< Second ink >>
The second ink according to the present invention is characterized by containing at least resin fine particles that inhibit the fixing of the colorant to the fiber, a water-soluble organic solvent, and water.

[Resin fine particles]
In the second ink according to the present invention, resin fine particles are added in order to prevent the colorant from adhering to the fibers in the subsequent step.

  The resin fine particles used in the second ink according to the present invention are not particularly limited. For example, polyacrylic acid, polymethacrylic acid, polyethylacrylic acid, styrene-butadiene copolymer, butadiene copolymer, acrylonitrile- Butadiene copolymer, chloroprene copolymer, crosslinked acrylic resin, crosslinked styrene resin, fluorine resin, vinylidene fluoride, benzoguanamine resin, phenol resin, polyolefin resin, cellulose, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer Polymer, polystyrene, styrene-acrylamide copolymer, n-isobutyl acrylate, acrylonitrile, vinyl acetate, acrylamide, silicone resin, polyvinyl acetal, polyamide, rosin resin, polyethylene, polycarbonate, salt Vinylidene resin, polyvinyl alcohol, cellulose resin, epoxy resin, vinyl acetate resin, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic copolymer, vinyl chloride resin, polyurethane, rosin ester, microgel, microemulsion, polyethylene wax , Montan wax, alcohol wax, synthetic oxide wax, α-olefin-maleic anhydride copolymer, carnauba wax and other animal and plant waxes, lanolin, paraffin wax, microcrystalline wax, etc., but are not limited thereto. Absent.

[Colorant]
As the colorant used in the present invention, all kinds of colorants are used. For example, acid dyes, direct dyes, reactive dyes, disperse dyes, pigments and the like are used. In particular, pigments are suitable for the present invention because of the ease of post-treatment.

(Water-soluble organic solvent)
The 2nd ink which concerns on this invention can contain the water-soluble organic solvent shown below as a specific example.

  Alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, diethylene glycol) Propylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine) , N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetet Amine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (eg, 2 -Pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (for example, dimethyl sulfoxide) and the like.

[Water-soluble polymer compound]
The second ink according to the present invention may contain a water-soluble polymer compound for the purpose of suppressing bleeding.

  When an appropriate water-soluble polymer compound is added, the degree of dry thickening immediately after landing of the ink is increased, the fluidity is lowered, and bleeding is suppressed.

  However, if resin fine particles and water-soluble polymer compound are added at a high concentration, precipitation may occur and injection stability may be significantly deteriorated. The type and amount of water-soluble polymer compound must be carefully selected. is there.

  Examples of water-soluble polymer compounds that can be added to the second ink include polyvinyl pyrrolidone, polyethylene glycol, ethylene oxide propylene oxide copolymer, glycerin polyethylene oxide adduct, glycerin polypropylene adduct, and diglycerin polyethylene oxide addition. Products, diglycerin polypropylene adducts, acrylic copolymer resins, and the like can be preferably used.

  Among them, the acrylic copolymer resin is preferable because it has a relatively small influence on the injection property and can be added in an amount necessary for expressing the effect of suppressing bleeding.

  As acrylic copolymer resin, what copolymerized the hydrophobic monomer and the hydrophilic monomer can be used preferably.

  Examples of hydrophobic monomers include acrylic acid esters (such as n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate), methacrylic acid esters (such as ethyl methacrylate, butyl methacrylate, glycidyl methacrylate), styrene. Etc.

  Examples of the hydrophilic monomer include acrylic acid, methacrylic acid, acrylamide, and the like, and those having an acidic group such as acrylic acid can preferably be those neutralized with resin fine particles after polymerization.

  As the molecular weight of these resins, those having an average molecular weight of 3000 to 30000 can be used. Preferably, 7000 to 20000 can be used.

  Resin having a Tg of about -30 ° C to 100 ° C can be used. Preferably, about -10 degreeC to 80 degreeC can be used. As the acid value of the resin, an acid value of about 90 mgKOH / g to 200 mgKOH / g can be particularly preferably used. As the polymerization method, it is preferable to use solution polymerization.

  The acidic group derived from the acidic monomer of the resin is preferably partially or completely neutralized with the resin fine particle component. As the neutralized resin fine particles in this case, alkali metal-containing resin fine particles, such as sodium hydroxide and potassium hydroxide, and amines (for example, ammonia, alkanolamine, alkylamine, etc.) can be used.

  In particular, neutralization with amines having a boiling point of less than 200 ° C. is preferable from the viewpoint of suppressing bleeding. In particular, those neutralized with ammonia are preferred.

  When the water-soluble polymer compound is added to the second ink, it is necessary that the polymer compound component is easily removed in the washing process in the fixing process after the aqueous ink is discharged to form an image on the fabric. If a large amount of the polymer compound component remains, it is not preferable because the touch and texture become hard. As the polymer compound component, those having high solubility in washing water or detergent are preferable.

  Furthermore, it is necessary to exist stably in the second ink, and to cause little occurrence of precipitation and change in physical properties such as viscosity under various storage environments.

  Even when the water-based ink is dried in the vicinity of the ejection opening of the head, it can be easily removed by re-dissolving, re-swelling, or re-dispersing with the water-based ink or the cleaning liquid, and maintenance is easy.

  The amount added to the second ink is preferably in the range of 1% by mass to 10% by mass, although it depends on the type and molecular weight of the polymer compound.

  The second ink according to the present invention can control the surface tension of the ink in order to penetrate deeply into a thick fabric and develop a color without unevenness.

  In this case, the surface tension is preferably controlled in the range of 20 mN / m to 35 mN / m. If it is less than 20 mN / m, the bleeding increases. If it is greater than 35 mN / m, the effect of penetrating to the deep part and coloring uniformly will be insufficient.

  As a method of adjusting the surface tension of the second ink within the above range, it can be adjusted by using an appropriate amount of a low surface tension solvent and an appropriate amount of a surfactant. In particular, it is preferable to adjust by using appropriate amounts of both a low surface tension solvent and a surfactant.

[Low surface tension solvent]
The low surface tension solvent preferably contains 10 to 30% by mass of a solvent having a surface tension of 25 to 40 mN / m. More preferably, it is an embodiment containing 10 to 30% by mass of a solvent having a surface tension of 25 to 35 mN / m.

  Examples of the solvent having a surface tension of 25 to 40 mN / m include water-soluble organic solvents such as glycol ether and 1,2-alkanediol.

  The solvent may be contained alone in an amount of 10 to 30% by mass, or a plurality thereof may be used and the total amount thereof may be contained in an amount of 10 to 30% by mass.

  The method for measuring surface tension is described in general interface chemistry and colloid chemistry reference books. For example, New Experimental Chemistry Course Vol. 18 (Interface and Colloid), The Chemical Society of Japan, Maruzen Co., Ltd. Issue: P.A. 68-117 can be referred to, and specifically, it can be determined by using a ring method (Dunoi method) or a vertical plate method (Wilhelmy method).

  The surface tension was measured using a surface tension meter CBVP type A-3 (Kyowa Science Co., Ltd.).

  Specific water-soluble organic solvents and surface tension values are shown below (the numerical values in parentheses are mN / m).

  Examples of glycol ethers include ethylene glycol monoethyl ether (28.2), ethylene glycol monobutyl ether (27.4), diethylene glycol monoethyl ether (31.8), diethylene glycol monobutyl ether (33.6), and triethylene glycol monobutyl ether. (32.1), propylene glycol monopropyl ether (25.9), dipropylene glycol monomethyl ether (28.8), tripropylene glycol monomethyl ether (30.0) and the like.

  Examples of the 1,2-alkanediol include 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol (28.1), 1,2-heptanediol, and the like.

[Surfactant]
Various surfactants can be used in the second ink according to the present invention. The surfactant that can be used in the present invention is not particularly limited, but examples thereof include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxy Nonionic surfactants such as ethylene alkylallyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. In particular, an anionic surfactant and a nonionic surfactant can be preferably used.

  In order to control the surface tension of the water-based ink according to the present invention to 20 mN / m or more and 35 mN / m or less, it is particularly preferable to contain a silicone surfactant or a fluorine surfactant.

  In the second ink according to the present invention, the surface tension of the second ink is preferably controlled to 20 mN / m or more and 35 mN / m or less in order to further infiltrate the resin fine particles into the deep part of the fabric. It is preferable to add a surfactant or a fluorosurfactant to control the desired surface tension.

<Silicone-based surfactant or fluorine-based surfactant>
The silicone-based surfactant is preferably a polyether-modified polysiloxane compound, and examples thereof include KF-351A and KF-642 manufactured by Shin-Etsu Chemical Co., and BYK345, BYK347, and BYK348 manufactured by Big Chemie.

  The fluorine-based surfactant means a compound in which a part or all of the fluorine-based surfactant is substituted with a fluorine atom instead of the hydrogen atom bonded to the carbon of the hydrophobic group of the normal surfactant. Of these, those having a perfluoroalkyl group in the molecule are preferred.

  Among the fluorine-based surfactants, certain types are traded under the trade name Megafac F from Dainippon Ink & Chemicals, and Surflon from Asahi Glass, Minnesota Mining and Under the trade name Fluorad FC from Manufacturing Company, under the trade name Monflor from Imperial Chemical Industry, and Zonyls from EI Dupont Nemeras & Company. It is commercially available under the trade name and also under the trade name Licobet VPF from Farbeberke Hoechst.

  Examples of nonionic fluorosurfactants include Megafax 144D manufactured by Dainippon Ink and Surflon S-141 and 145 manufactured by Asahi Glass Co., and amphoteric fluorosurfactants. Examples of the agent include Surflon S-131 and 132 manufactured by Asahi Glass Co., Ltd.

[Other additives]
A pH adjuster and a solid humectant can be added to the second ink as necessary.

<Inkjet dyeing method>
The first ink and the second ink according to the present invention are applied directly from the inkjet head to the fabric. The order of applying the first ink and the second ink can be arbitrarily selected. A method of applying the first ink to the fabric and then applying the second ink, a method of applying the second ink, and then applying the first ink, or a method of applying the first ink and the second ink simultaneously can be selected.

  Further, in the inkjet dye-resisting method of the present invention, coloring called background dyeing can be performed on the fabric in advance or later, and this may be performed by any method such as an inkjet method, a screen printing method, or a dip dyeing method. .

[Method for Applying First Ink and Second Ink to Fabric]
The method of applying the first ink to the fabric and then applying the second ink is the most preferable method for suppressing bleeding. Specifically, the head for the first ink is provided on the upstream side in the fabric conveyance direction. In this method, a head for the second ink is arranged on the downstream side, and the first ink and then the second ink are sequentially printed. In this method, there is room for the first ink to permeate into the fabric and further to dry, so that the bleeding is least likely to occur during image recording with the subsequent second ink.

  In order to promote drying of the first ink, it is preferable to provide a drying zone between the head position for the first ink and the head position for the second ink from the viewpoint of suppressing bleeding.

  A method of simultaneously applying the first ink and the second ink is also preferable because it has the advantage of reducing the apparatus size. A plurality of heads can be arranged on one carriage, and a first ink head and a second ink head can be mounted therein and applied simultaneously.

  The application region of the first ink can be arbitrarily selected. The first ink can be applied to the entire area of the fabric, or can be applied only to a specific area. The first ink suppresses bleeding of the image, and may be basically applied only to the image portion to which the second ink is applied. This has the merit of reducing the consumption of the first ink and lowering the production cost. Further, it is preferable to avoid applying the first ink to a white background because it may lead to contamination of the white background. Further, it is also a preferable form that the amount of the first ink is increased or decreased according to the amount of the second ink applied. In this case, it is preferable to increase the first ink application amount as the ink amount increases.

More specifically, the first ink is not applied to a portion where the second ink is not substantially applied, and the first ink is applied to an area where the total amount of the second ink is greater than 20 ml / m ² for each pixel area. ink minimum 12 ml / ^{m 2} is applied to, the second ink application amount is 20 ml / ^{m 2} less than in the region, applying the first ink in the range of 4 ml / ^{m 2} of 20 ml / ^{m 2} in response to the second ink This is a preferred embodiment.

  The amount of the first ink applied can be increased or decreased depending on the type and concentration of the water-soluble polymer compound in the first ink.

The first ink application amount, be 40 ml / ^{m 2} applied from 10 ml / ^{m 2} with respect to the fabric, from the viewpoint of bleed suppression. Of course, the amount of the first ink applied can be determined at an arbitrary ratio according to the amount of the second ink applied, and the first ink may not be applied to the white background where the second ink is not applied.

  The first ink can be supplied from one or more heads. In particular, it is preferable to supply from a plurality of heads from the viewpoint that unevenness is hardly generated in the applied amount of the first ink.

  When the first ink is applied from a plurality of heads, a plurality of types of first inks may be introduced and applied to each head.

[Fabric heating]
In the ink jet discharging method or ink jet resist method of the present invention, the first ink and the second ink can be applied by heating the fabric. As a heating method, for example, a heater can be arranged around the lower part of the platen and heated to an arbitrary temperature.

  By heating when the first ink is applied, the permeability of the first ink can be controlled. In particular, heating is preferable when it is desired to leave the first ink component near the surface. Also, the drying of the first ink is accelerated, which is preferable from the viewpoint of suppressing bleeding.

  The fabric surface temperature can be heated in the range of 35 ° C to 70 ° C.

  By heating at the time of applying the second ink, it is possible to suppress bleeding and control permeation. The fabric surface temperature can be heated in the range of 35 ° C to 70 ° C.

[Dry]
In the case where the second ink is applied after the first ink is applied, drying is preferably performed after the first ink is applied. In particular, it is particularly preferable to provide a drying zone and evaporate the moisture and the volatile solvent applied by the first ink.

  As a drying method, there are a method of contacting a heated member from the back surface or the front surface, a method of irradiating with an infrared heater, and the like. In these methods, it is preferable to use a blower together to further increase the drying efficiency.

  The pre-dried fabric is preferably subjected to steaming. The conditions may be determined in consideration of the type of fabric and the like, but in an environment with a humidity of 50 to 100% (more preferably 80 to 100%) and a temperature of 90 to 120 ° C (preferably 95 to 105 ° C). 3 to 120 minutes (preferably 5 to 40 minutes). Further, after that, it is preferable to wash with warm water containing a surfactant (preferably a nonionic surfactant). The printed fabric subjected to such post-processing has excellent color development and fastness, and less water-based ink bleeding.

[Fabric]
As the fabric used in the present invention, a fabric containing fibers that can be colored by the used colorant is used. For example, reactive dyes include cotton, wool, and silk. When a pigment is used as the colorant, it is possible to color a fabric using all kinds of fibers. In addition, ink-jet pretreatment for absorbing ink is not necessary for the fabric, but general pretreatment used in usual dyeing processes such as hair baking, desizing, refining, and bleaching can be performed.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<Preparation of ink set>
[Preparation of first ink]
(Preparation of the first ink 1)
The following additives were added, mixed and dissolved, and then filtered through a 0.8 μm membrane filter to prepare the first ink 1.

Water-soluble polymer compound: polyvinylpyrrolidone (PVP (K15), manufactured by Tokyo Chemical Industry Co., Ltd.)
6% by mass
Liquid humectant: 20% by mass of propylene glycol (PG)
Liquid humectant: Glycerin (Gly) 5% by mass
Solid moisturizer: urea 10% by mass
Water-soluble cationic polymer: diallylamine (DAA) 1% by mass
Ion exchange water was added to finish 100% by mass.

(Preparation of first inks 2 to 19)
First inks 2 to 19 were prepared in the same manner as in the preparation of the first ink 1 except that the composition of each additive was changed as shown in Table 1.

  The details of each additive described in abbreviations in Table 1 are as follows. Moreover, the numerical value of Table 1 represents the mass%.

<Water-soluble polymer compound>
PVP15: Polyvinylpyrrolidone K15, manufactured by Tokyo Chemical Industry Co., Ltd. PVP30: Polyvinylpyrrolidone K30, manufactured by Tokyo Chemical Industry Co., Ltd. PEG: Polyethylene glycol, Mw600, manufactured by Kanto Chemical Co., Ltd. : SC-E450, polyethylene oxide adduct of diglycerin, manufactured by Sakamoto Pharmaceutical Co., Ltd. P450: SC-P450, polypropylene oxide adduct of diglycerin, manufactured by Sakamoto Pharmaceutical Co., Ltd. Gly450: glycerin (EO) 450, ethylene of glycerin Oxide adduct, ethylene oxide molecular weight 450
HEC: Hydroxyethyl cellulose CMC: Carboxymethyl cellulose <Liquid humectant>
PG: Propylene glycol, manufactured by Kanto Chemical Co. Gly: Glycerin, manufactured by Kanto Chemical Co. <Solid moisturizer>
* 1: Dimethylurea <Water-soluble cationic polymer>
DAA: diallylamine, PAS-21Cl, Nittobo DMAA: dimethyldiallylamine, PAS-M-1L, Nittobo AMAC: diallyldimethylammonium chloride, PAS-H-1L, Nittobo [Preparation of second ink ]
(Preparation of the second ink 1)
The following additives were added, mixed, and dissolved, followed by filtration through a 0.8 μm membrane filter to prepare the second ink 1.

Water-soluble organic solvent: ethylene glycol (EG) 10% by mass
Water-soluble organic solvent: Propylene glycol (PG) 25% by mass
Resin fine particles: AQUACER 515, polyethylene wax emulsion (active ingredient 35%), Big Chemie Co., Ltd. 3% by mass
Ion exchange water was added to finish 100% by mass.

(Preparation of the second ink 2)
The following additives were added, mixed and dissolved, and then filtered through a 0.8 μm membrane filter to prepare the second ink 2.

Water-soluble organic solvent: ethylene glycol (EG) 10% by mass
Water-soluble organic solvent: Propylene glycol (PG) 25% by mass
Resin fine particles: AQUACER 515 (polyethylene wax emulsion (active ingredient 35%), Big Chemie Japan Co., Ltd.) 3% by mass
Dispersion A 50% by mass
Ion exchange water was added to finish 100% by mass.

<Preparation of dispersion A>
Acid carbon black MA-7 (Mitsubishi Chemical) 10% by mass
BYK-190 Big Chemie (active ingredient 40%) 12.5% by mass
Propylene glycol (PG) 25% by mass
Glycerin (Gly) 10% by mass
Olfine E1010 (acetylene glycol-based activator, manufactured by Shin-Etsu Chemical Co., Ltd.)
0.5% by mass
Ion exchange water was added to finish 100% by mass.

  After the above additives were added and mixed, bead mill dispersion was performed using a MiniCer disperser manufactured by Ashizawa Finetech. Dispersion was performed using 0.5 mm zirconia beads at a peripheral speed of 12 m / s. Dispersion was terminated when the average particle size by light scattering method reached 150 nm, and dispersion A was obtained.

(Preparation of second inks 3 to 5)
In the preparation of the second ink 1, in place of AQUACER 515 as resin fine particles, the same amount of AQUACER 498 (paraffin wax emulsion (active ingredient 50%), Big Chemie Japan Co., Ltd.), AQUACER 537 (polypropylene resin fine particles, Big Chemie) Co., Ltd.) and JONCRYL WAX22 (34% active ingredient, BASF Japan Ltd.) were used to prepare second inks 3 to 5 in the same manner.

[Preparation of ink sets 1 to 26]
Ink sets 1 to 26 were prepared by combining the prepared first inks 1 to 19 and second inks 1 to 5 as shown in Table 2.

<< Production of Fabric: Production of Cotton Test Cloth >>
A cloth 122 g / m ² (color dye company) with cotton broad sill that was not subjected to inkjet pretreatment (gluing) was used as a cotton test cloth.

<Creating a print>
(Evaluation printer)
Of the carriage of the first head 1 on which the four heads of the evaluation printer shown in FIG. 1 are mounted, two heads are filled with the first ink described in Table 2. Next, of the carriage of the second head 2 mounted with six heads, two heads described in Table 2 were filled in two heads.

(Print)
The cotton test cloth, which was the fabric produced above, was set in the printer for evaluation shown in FIG. The conveyed fabric was uniformly applied to the entire surface of the fabric under the condition of 9 ml / m ² from each of the two heads constituting the first head 1. Next, among the six heads constituting the second head 2, image recording was performed by applying the second ink from two heads. As a recorded image, a solid image of 10 cm × 10 cm of the second ink was printed. This image has a 100% duty and a second ink application amount of about 11 ml / m ² .

  In addition, a drying zone was provided between the first head 1 and the second head 2, and the fabric was heated to 55 ° C. by the heater H2 (4) to dry the first ink applied on the fabric.

  Furthermore, at the time of recording the first ink and the second ink, the fabric was heated to 40 ° C. using platen heaters H1 (3) and H3 (5) provided at the bottom of the fabric. However, the heater H1 (3) was not used in the production of the print sample 23, and the heater H1 (3) and the heater H3 (5) were not used in the production of the print sample 24.

(Post-processing)
After the fabric was printed according to the above method, it was dried at 80 ° C. for 5 minutes.

  Next, solid printing was performed using TP-V manufactured by Konica Minolta, which is an inkjet printer for textile printing, and a reactive dye ink, followed by drying at 80 ° C. for 5 minutes to perform fixing treatment, and print samples 1 to 26 were obtained.

<Reactive dye ink>
The following additives were added, mixed and dissolved, and then filtered through a 0.8 μm membrane filter to prepare a reactive dye ink.

C. I. Reactive Red 24 10% by mass
Propylene glycol (PG) 25% by mass
Glycerin (Gly) 10% by mass
Olfine E1010 (supra) 0.5% by mass
Ion exchange water was added to finish 100% by mass.

<Adhesion treatment>
The cotton test cloth was subjected to a color development treatment at 120 ° C. for 10 minutes using an HT steamer. Thereafter, as washing treatment, water washing was performed for 10 minutes, 80 ° C. hot water washing for 10 minutes, 90 ° C. soaping using 2 g / L of a nonionic detergent, 80 ° C. hot water washing for 10 minutes, and water washing for 10 minutes. Then, it was dried at 50 ° C. until there was no water.

<< Evaluation of Printed Sample >>
Each of the produced print samples was subjected to the following evaluations.

(Evaluation of smear resistance)
The periphery of the solid image of each of the prepared print samples was visually observed, and the bleeding resistance was evaluated according to the following criteria.

5: No blurring is observed in the peripheral area of the image 4: Slight blurring is observed in the peripheral area of the image, but the quality is good 3: Slight blurring is observed in the peripheral area of the image, but practical use 2: acceptable quality 2: Obvious blurring is observed at the periphery of the image, which is a problem in practical use 1: Vigorous blurring is observed at the periphery of the image; Yes (Evaluation of unevenness resistance)
The density uniformity of the solid image of each of the prepared print samples was visually observed, and unevenness resistance was evaluated according to the following criteria.

5: No unevenness is observed in the solid image 4: Unevenness is not confirmed in the solid image part, but the left and right edges are different in density 3: Uneven noticeable unevenness is observed in the solid image part 2 : Occurrence of obvious unevenness in the solid image portion is observed in several places 1: Very large unevenness in the solid image portion The results obtained as described above are shown in Table 2.

  As is clear from the results shown in Table 2, the printed matter produced using the first ink and the second ink having the configuration defined in the present invention is more resistant to bleeding and unevenness of the formed image than the comparative example. It can be seen that a high-quality printed matter can be obtained.

Example 2
<Preparation of ink set>
Ink set 1 and ink set 23 prepared in Example 1 were used.

<< Fabric >>
The cotton test fabric produced in Example 1 was used as the fabric.

<Creating a print>
In the print creation method described in the first embodiment, the first ink and the second ink constituting the ink set 1 and the ink set 23 are filled with two of the six heads of the second head, and the first ink is filled in the two heads. Then, print samples 27 to 29 were obtained in the same manner except that two heads were filled with the second ink and the first ink and the second ink were simultaneously ejected onto the fabric.

<< Evaluation of Printed Sample >>
For each of the prepared print samples, bleeding resistance and unevenness resistance were evaluated in the same manner as in the method described in Example 1, and the results obtained are shown in Table 3.

  As is clear from the results shown in Table 3, the printed matter produced by simultaneously ejecting the first ink and the second ink having the configuration defined in the present invention is more resistant to bleeding of the formed image than the comparative example. It can be seen that high-quality printed matter is obtained with excellent unevenness resistance.

Example 3
<Preparation of ink set>
Ink sets 1, 2, 23 and 24 prepared in Example 1 were used.

<< Production of Fabric: Production of Wool Test Cloth >>
Wool tropical 180g / m ² (color dye company) which has not been subjected to inkjet pretreatment (gluing) is used as a wool test cloth.

<Creating a print>
In the same manner as described in Example 1, images were recorded on the fabric to obtain print samples 30 to 33. However, the fixing conditions were changed as follows.

<Adhesion treatment>
The wool test cloth was subjected to a color development treatment at 100 ° C. for 40 minutes using a rocket steamer. Thereafter, as washing treatment, water washing was performed for 10 minutes, 80 ° C. hot water washing for 10 minutes, 90 ° C. soaping using 2 g / L of a nonionic detergent, 80 ° C. hot water washing for 10 minutes, and water washing for 10 minutes. Then, it was dried at 50 ° C. until there was no water.

<< Evaluation of Printed Sample >>
Each of the created print samples was evaluated for bleeding resistance and unevenness resistance in the same manner as in the method described in Example 1, and the obtained results are shown in Table 4.

  As is apparent from the results shown in Table 4, the printed matter produced using the first ink and the second ink having the configuration defined in the present invention is more resistant to bleeding and unevenness of the formed image than the comparative example. It can be seen that high quality prints can be obtained.

Example 4
<Preparation of ink set>
Ink sets 1, 2, 23 and 24 prepared in Example 1 were used.

<< Production of Fabric: Production of Silk Test Cloth >>
Silk feather double 52.5 g / m ² (color dye company) that had not been subjected to inkjet pretreatment (gluing) was used as a silk test cloth.

<Creating a print>
In the same manner as in the method described in Example 1, images were recorded on the fabric, and print samples 34 to 37 were obtained. However, the fixing conditions were changed as follows.

<Adhesion treatment>
The silk test cloth was subjected to a color development treatment at 100 ° C. for 40 minutes using a rocket steamer. Thereafter, as washing treatment, water washing was performed for 10 minutes, 80 ° C. hot water washing for 10 minutes, 90 ° C. soaping using 2 g / L of a nonionic detergent, 80 ° C. hot water washing for 10 minutes, and water washing for 10 minutes. Then, it was dried at 50 ° C. until there was no water.

<< Evaluation of Printed Sample >>
Each of the created print samples was evaluated for bleeding resistance and unevenness resistance in the same manner as described in Example 1, and the obtained results are shown in Table 5.

  As is apparent from the results shown in Table 5, the printed matter produced using the first ink and the second ink having the configuration defined in the present invention is more resistant to blurring and unevenness of the formed image than the comparative example. It can be seen that high quality prints can be obtained.

1 First head 2 Second head 3 Heater H1
4 Heater H2
5 Heater H3
6, 7 Roller

Claims (8)

  An inkjet ink set for fabric, comprising: a first ink containing water, a liquid humectant, and a water-soluble polymer compound; and a second ink containing water, resin fine particles, and a water-soluble organic solvent. .   The inkjet ink set for cloth according to claim 1, wherein the first ink contains a solid humectant.   The water-soluble polymer compound is polyvinyl pyrrolidone, polyethylene glycol, ethylene oxide propylene oxide copolymer, glycerin polyethylene oxide adduct, glycerin polypropylene adduct, diglycerin polyethylene oxide adduct, and diglycerin polypropylene adduct. The total amount of the water-soluble polymer compound is 1% by mass or more and less than 10% by mass as a solid content with respect to the total mass of the first ink. Item 3. An inkjet ink set for fabric according to Item 1 or 2.   The inkjet ink set for cloth according to any one of claims 1 to 3, wherein the first ink contains a water-soluble cationic polymer.   An inkjet dye-resisting method comprising applying a colorant after applying the first ink and the second ink to a fabric using the inkjet ink set for fabric according to any one of claims 1 to 4. .   The inkjet dyeing method according to claim 5, wherein the first ink is applied while heating the fabric.   The printer used to apply the first ink and the second ink to the fabric is a printer in which the first ink head and the second ink head are arranged on the same carriage, and one scan is performed. The inkjet dyeing method according to claim 5, wherein the first ink and the second ink are applied onto the fabric.   The inkjet dyeing method according to claim 5 or 7, wherein the first ink and the second ink are applied while heating the fabric.

Images