JP2018053394A - Inkjet printing method, ink set for inkjet printing and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet printing method excellent in color development and capable of forming images excellent in washing fastness at low cost in an inkjet printing with aim for printing on fabrics.SOLUTION: There is provided an inkjet printing method using an aqueous ink and a reaction ink, the aqueous ink contains at least an emulsion, a water soluble organic solvent, a pigment and water, the reaction ink contains a coagulant consisting of a water soluble cation polymer having primary amine group, a water soluble organic solvent and water, the reaction ink is printed on fabrics by an inkjet in a part for forming images and, at same time, the aqueous ink is printed in the image formation part and they get in contact on the fabrics.SELECTED DRAWING: None

Description

    The present invention relates to an ink jet textile printing method, an ink set for ink jet textile printing, and a printed matter.

    Conventionally, as a method for printing on a fabric called textile (hereinafter referred to as textile printing), printing has been performed by producing a plate for each pattern to be printed, such as rotary flat screen textile printing or transfer textile printing. On the other hand, there is an ink jet method as one of methods for recording an image, characters, patterns, and the like (hereinafter collectively referred to as an image) on a recording medium using ink. So-called digital textile printing using ink used in the ink jet system (hereinafter referred to as ink jet ink) has attracted attention.

  In the ink jet textile printing method, in the conventional system in which the coloring material used for the ink jet ink uses a dye, the waste water treatment at the time of processing is required for the pre-treatment and post-treatment at the time of textile printing.

  Water-based pigment inks using pigments are attracting attention because they are simple in pre-treatment and post-treatment during textile printing and do not require waste water treatment during processing.

  The ink-jet printing method (ink-jet printing method) has restrictions in terms of ink viscosity and ejection properties compared to conventional printing methods such as screen printing, so the colorant concentration and resin concentration can be reduced. Cannot be set too high. For this reason, the above-mentioned problems such as fastness and color developability are noticeable.

  For example, Patent Document 1 proposes an ink-jet printing method in which bleeding is prevented and a clear image can be obtained by using a pre-treated fabric on which a dye retaining agent is previously attached (Japanese Patent Laid-Open No. 61). -55277).

  Patent Document 2 proposes a method for pre-processing a printing fabric in order to improve the fixing property to the fabric. Examples of the pretreatment liquid include a liquid containing a polyvalent metal salt, polyallylamine or a derivative thereof.

  According to the example of Patent Document 2, after printing on a fabric using a pretreatment liquid, printing is performed using a material dried at 130 ° C. for 5 minutes. In this case, a drying process will be performed once after the pretreatment, and when performing printing on a scroll-like fabric, generally called roll-to-roll, apart from a printing process for printing an actual image or pattern, It is necessary to prepare in advance a pre-processed raw material that has been subjected to processes such as unwinding of the fabric, treatment with a pre-treatment liquid, drying, and winding, and there is concern about an increase in man-hours and an increase in cost.

JP-A-61-55277 JP 2011-31479 A

  On the other hand, as a problem of pigment printing, it is inferior in fastness such as discoloration during washing because it is a printing method in which the resin component in the ink is fixed on the surface of the fabric to be dyed as compared with a dye system for directly dyeing fibers.

  In addition, since the pigment penetrates into the fiber (fixes color) before fixing on the fiber surface, the color forming source does not exist on the surface, which causes a decrease in color developability compared to the dye.

[1] An inkjet printing method using a water-based ink and a reactive ink,
The water-based ink includes at least an emulsion, a water-soluble organic solvent, a pigment, and water,
The reactive ink includes a flocculant composed of a water-soluble cationic polymer having a primary amine group, a water-soluble organic solvent, and water.
An ink-jet printing method characterized in that a reactive ink is printed on a fabric by inkjet on a portion where an image is to be formed, and at the same time, an aqueous ink is printed on an image forming portion and brought into contact with the fabric.
[2] The inkjet printing method according to claim 1, wherein the water-soluble cationic polymer has a weight average molecular weight of 5,000 to 20,000 as determined by GPC (gel permeation chromatography).
[3] The inkjet printing method according to claim 1 or 2, wherein the water-soluble cationic polymer is polyallylamine or polyvinylamine.
[4] The inkjet printing method according to any one of claims 1 to 3, wherein the reactive ink contains 1,2-alkanediol having 7 to 10 carbon atoms.
[5] The inkjet printing method according to any one of [1] to [4], wherein the reactive ink does not contain a surfactant.
[6] The inkjet printing method according to any one of 1 to 5, wherein the pigment is dispersed by a surfactant.
[7] The ink-jet printing method according to any one of [1] to [6], wherein the fabric is a polyester alone or a blend of polyester and other fibers.
[8] An inkjet printed matter printed by the method according to any one of claims 1 to 7.
[9] An inkjet ink set having a water-based ink and a reactive ink,
The water-based ink includes at least an emulsion, a water-soluble organic solvent, a pigment, and water. The reaction ink includes a flocculant composed of a water-soluble cationic polymer having at least a primary amine group, and a water-soluble organic solvent. Ink-jet ink set comprising water.

ADVANTAGE OF THE INVENTION According to this invention, the ink-jet textile printing method which can improve the bleeding and coloring property to a fabric, and can form the image excellent in wash fastness can be provided. Furthermore, the processing time can be reduced and the wastewater used in the pretreatment process can be reduced.

  Hereinafter, an embodiment of the present invention (hereinafter also referred to as this embodiment) will be described in detail. The present invention is not limited to the following contents.

  In the textile printing method of the present invention, first, a reactive ink containing an aggregating agent, which will be described later, is printed on a portion of the fabric on which an image is formed, and thereafter water-based inks of various colors are printed and contacted on the fabric. Thus, the flocculant and the water-based ink react to suppress bleeding of the pigment component contained in the water-based ink and penetration into the inside of the fabric (color settling), thereby obtaining high color developability.

  After the reaction ink containing the flocculant is printed by the ink jet printer, it is possible to wind up the material once dried through the platen or the drying heater and print the water-based ink again. In consideration, it is preferable that the water-based ink is printed continuously without winding the fabric after printing the reactive ink.

  The print density when the reactive ink is printed on the fabric is not particularly limited but is preferably set to a print density of 30 to 100%.

<Water-based ink>
The water-based ink includes an emulsion, a surfactant, a water-soluble organic solvent, a pigment, and water.

(Emulsion)
An emulsion is a component that forms an image having excellent coating properties such as scratch resistance by improving the film-forming property of an aqueous ink. In the inkjet ink set according to the present embodiment, the water-based ink does not contain a film-forming aid. Therefore, the emulsion does not easily form a film by drying at room temperature, and therefore, when the aqueous ink is ejected from the inkjet head, it is difficult to form a film near the nozzle. As a result, it is possible to ensure the discharge stability of the water-based ink.

  The glass transition temperature of the emulsion is preferably 50 ° C. or less. More preferably, it is 30 degrees C or less. A glass transition temperature of 50 ° C. or higher is not preferable because the texture of the printed material is lowered and the flexibility of the fabric is impaired. Examples of the resin constituting the emulsion include styrene, tetrahydrofurfuryl acrylate, butyl (meth) acrylate, (α, 2,3 or 4) -alkylstyrene, (α, 2,3 or 4) -alkoxystyrene, 3, 4-dimethylstyrene, α-phenylstyrene, divinylbenzene, vinylnaphthalene, dimethylamino (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropylacrylamide, N, N-dimethylaminoethyl acrylate, acryloylmorpholine, N , N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ethylhexyl (meth) Acrylate, other alkyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, (meth) acrylate of diethylene glycol or polyethylene glycol having ethoxy group, (meth) acrylate of diethylene glycol or polyethylene glycol having propoxy group, diethylene glycol having butoxy group Or polyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyalkyl (meth) acrylate, other fluorine-containing (meth) acrylates, Examples include chlorine-containing (meth) acrylates and silicon-containing (meth) acrylates.In addition, when introducing a crosslinked structure in addition to a monofunctional group such as (meth) acrylamide, maleic acid amide, (meth) acrylic acid, (mono, di, tri, tetra, poly) ethylene glycol di (meth) acrylate, Di (meth) acrylate such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, trimethylolpropane tri (meth) acrylate , Glycerin (di, tri) (meth) acrylate, di (meth) acrylate of ethylene oxide adducts of bisphenol A or F, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate and the like.

  The content of the emulsion is preferably 3 to 30 parts by weight with respect to 100 parts by weight of the entire aqueous ink. When the content is less than 3 parts by weight, a film having sufficient film strength may not be formed. On the other hand, if the content exceeds 30 parts by weight, the viscosity of the water-based ink may become too high, and ejection failure may occur during ejection by inkjet. The content of the emulsion is more preferably 5 parts by weight or more and more preferably 20 parts by weight or less with respect to 100 parts by weight of the entire aqueous ink.

(Surfactant)
The surfactant is a component that improves wettability to the fabric.

  Examples of the surfactant include silicon-based surfactants, fluorine-based surfactants, acetylene glycol-based surfactants, and polyoxyalkylene alkyl ethers.

  The silicon surfactant is preferably a polysiloxane compound. Examples of the polysiloxane compound include polyether-modified siloxane, polyether-modified polydimethylsiloxane, and polyether-modified organosiloxane. Specifically, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (above trade names, manufactured by Big Chemie Japan Co., Ltd.), KF-351A, KF -352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF -6012, KF-6015, KF-6017 (above trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more.

  The content of the surfactant is preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the entire aqueous ink. When the content is less than 0.1 part by weight, the water-based ink may not be sufficiently wetted and spread with respect to the substrate. On the other hand, when the content exceeds 5.0 parts by weight, an excessive surfactant may bleed on the surface of the coating film, and the adhesion of the aqueous ink to the substrate may be inferior. The content of the surfactant is more preferably 0.5 parts by weight or more and more preferably 3.0 parts by weight or less with respect to 100 parts by weight of the entire aqueous ink.

(Water-soluble organic solvent)
The water-soluble organic solvent is a component that adjusts the drying property of the water-based ink and the wettability with respect to the substrate. The content of the water-soluble organic solvent is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the entire aqueous ink. When the content is less than 5 parts by weight, the drying speed may become too fast and the discharge stability may be poor. On the other hand, if the content exceeds 40 parts by weight, the amount of volatile organic compound (VOC) emitted may be greater than the regulated value. The content of the water-soluble organic solvent is more preferably 10 parts by weight or more and more preferably 30 parts by weight or less with respect to 100 parts by weight of the entire aqueous ink.

  The water-soluble organic solvent is preferably a water-soluble organic solvent that is difficult to plasticize the emulsion. Such a water-soluble organic solvent is preferably a polyhydric alcohol and / or a pyrrolidone derivative. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 1, 5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 3,5-dimethyl-3-hexyne-2,5-diol, 2,5-hexanediol, hexylene glycol, 1,6- Hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl- , 3-pentanediol, 2,5-dimethyl-2,5-hexanediol, 1,4-cyclohexanedimethanol, and 2,2 thiodiethanol. Examples of pyrrolidone derivatives include 2-pyrrolidone and N-methyl-2-pyrrolidone. Examples of other water-soluble organic solvents include 3-pyridyl carbinol and sulfolane. Among these, considering the boiling point and safety, 1,3-butanediol, 2-methyl-1,3-propanediol, and propylene glycol are preferable.

(Pigment)
Conventionally known inorganic pigments and organic pigments can be used as the pigment. These may be used alone or in combination of two.

  Examples of the inorganic pigment include titanium oxide, zinc oxide, zinc oxide, tripone, iron oxide, aluminum oxide, silicon dioxide, kaolinite, montmorillonite, talc, barium sulfate, calcium carbonate, silica, alumina, cadmium red, and red rose. Molybdenum red, chrome vermilion, molybdate orange, yellow lead, chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, pyridiane, cobalt green, titanium cobalt green, cobalt chrome green, ultramarine blue, ultramarine blue, bitumen , Cobalt blue, cerulean blue, manganese violet, cobalt violet, mica and the like. These may be used alone or in combination of two or more.

  Examples of the organic pigment include azo, azomethine, polyazo, phthalocyanine, quinacridone, anthraquinone, indigo, thioindigo, quinophthalone, benzimidazolone, and isoindoline. Further, as the organic pigment, carbon black made of acidic, neutral or basic carbon, hollow particles of crosslinked acrylic resin, and the like can be used. These may be used alone or in combination of two or more.

  The pigment content is preferably 0.1 parts by weight or more and more preferably 0.3 parts by weight or more with respect to 100 parts by weight of the entire aqueous ink. Moreover, it is preferable that it is 15 weight part or less, and it is more preferable that it is 10 weight part or less.

(water)
Examples of water include ion exchange water, distilled water, tap water, and well water. Among these, ion-exchanged water is preferable from the viewpoint of relatively few impurities and being available at low cost.

  If necessary, the water-based ink may contain other additives as long as the effects of the present invention are not impaired. Examples of other additives include antifungal agents, chelating agents, pH adjusters, and rust inhibitors.

  The water-based ink is not particularly limited. For example, the emulsion, the surfactant, the water-soluble organic solvent, the pigment, the water, and, if necessary, other additives are mixed and stirred. It can manufacture by mixing uniformly using etc.

  The water-based ink produced in this manner preferably has a viscosity at 25 ° C. of 1 to 15 mPa · s or less from the viewpoint of improving the dischargeability from the inkjet head. The viscosity of the water-based ink can be measured using an R100 type viscometer in accordance with JIS Z 8803.

<Reactive ink>
The reactive ink includes a flocculant made of a water-soluble cationic polymer having at least a primary amine group, a water-soluble organic solvent, and water. The reactive ink preferably does not contain a surfactant. The water-based ink contains a surfactant as an essential component. Therefore, if the reactive ink also contains a surfactant, the adhesion of the formed image may be inferior.

  Examples of the surfactant not contained in the reactive ink include nonionic surfactants, cationic surfactants, and amphoteric surfactants.

  Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, Ether surfactants such as oxyethylene alkyl ether and polyoxyalkylene alkyl ether (polyoxypropylene polyoxyethylene alkyl ether), polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laur Rate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene mono Reeto, ester surfactant such as polyoxyethylene stearate, fluorine-containing surfactants such as fluorine alkyl esters, such as containing a silicone surfactant such as the polyether silicone.

  Examples of cationic surfactants include alkylamine salts such as coconut amine acetate and stearylamine acetate, quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and alkylbenzyldimethylammonium chloride, laurylbetaine, and stearylbetaine. And alkylbetaines such as amine oxides such as lauryldimethylamine oxide.

  Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives, etc. Is mentioned.

(Flocculant)
The aggregating agent is a component that aggregates the emulsion and the pigment contained in the aqueous ink. The flocculant in the present invention is required to be a water-soluble cationic polymer having a primary amine group.

Examples of the water-soluble cationic polymer include polyallylamine, polyvinylamine, and polyethyleneimine. These may be used alone or in combination of two or more.
The flocculant does not contain a surfactant.

  The content of the flocculant is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the entire reactive ink. When the content is less than 1 part by weight, the cohesive force is weak and a sufficient blurring prevention effect may not be obtained. On the other hand, when the content exceeds 10 parts by weight, the coating film properties such as water resistance and solvent resistance of the coating film may be inferior. The content of the flocculant is more preferably 2 parts by weight or more, and more preferably 6 parts by weight or less, with respect to 100 parts by weight of the entire reactive ink.

  The weight average molecular weight of the flocculant is preferably in the range of 5,000 to 20,000. When the weight average molecular weight is 5,000 or less, there is a concern that the aggregated unit when aggregated with an emulsion or pigment with water-based ink is reduced, and physical properties such as washing fastness are lowered. Moreover, when it is 20,000 or more, there is a concern that defective ejection is likely to occur when the reactive ink is ejected from the inkjet head. The weight average molecular weight of the flocculant is more preferably 8,000 or more, and more preferably 18,000 or less.

(Water-soluble organic solvent)
The water-soluble organic solvent is a component that adjusts the drying property of the reaction ink and the wettability of the fabric, like the water-based ink. The content of the water-soluble organic solvent is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the entire aqueous ink. When the content is less than 5 parts by weight, the drying speed may become too fast and the discharge stability may be poor. On the other hand, if the content exceeds 40 parts by weight, the amount of volatile organic compound (VOC) emitted may be greater than the regulated value. The content of the water-soluble organic solvent is more preferably 10 parts by weight or more and more preferably 30 parts by weight or less with respect to 100 parts by weight of the entire aqueous ink.

  The water-soluble organic solvent is preferably a water-soluble organic solvent that is difficult to plasticize the emulsion. Such a water-soluble organic solvent is preferably a polyhydric alcohol and / or a pyrrolidone derivative. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 1, 5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 3,5-dimethyl-3-hexyne-2,5-diol, 2,5-hexanediol, hexylene glycol, 1,6- Hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl- , 3-pentanediol, 2,5-dimethyl-2,5-hexanediol, 1,4-cyclohexanedimethanol, and 2,2 thiodiethanol. Examples of pyrrolidone derivatives include 2-pyrrolidone and N-methyl-2-pyrrolidone. Examples of other water-soluble organic solvents include 3-pyridyl carbinol and sulfolane. Among these, considering the boiling point and safety, 1,3-butanediol, 2-methyl-1,3-propanediol, and propylene glycol are preferable.

(1,2-alkanediol)
In the present invention, the water-soluble organic solvent of the reaction ink preferably contains 1,2-alkanediol. 1,2-alkanediol is a component that adjusts the drying speed of the reactive ink and increases the wettability to the substrate. Examples of the 1,2-alkanediol include 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, and 1,2. -Octanediol and the like. These may be used alone or in combination of two or more. Among these, 1,2-heptanediol and 1,2-octanediol are preferable from the viewpoint of improving the boiling point and wettability with respect to the substrate.

  The content of the 1,2-alkanediol is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the entire reaction ink. If the content is less than 0.1 part by weight, the reactive ink may not have sufficient wettability. On the other hand, if the content exceeds 10 parts by weight, the 1,2-alkanediol may destabilize the reaction ink and cause liquid separation. In addition, the amount of volatile organic compound (VOC) emissions may be greater than the regulation value. The content of the 1,2-alkanediol is more preferably 1 part by weight or more and more preferably 3 parts by weight or less with respect to 100 parts by weight of the entire reaction ink.

(Glycol ether solvent)
In the present invention, the water-soluble organic solvent of the reactive ink may contain a glycol ether solvent. The glycol ether solvent is a component that improves the film-forming property of the emulsion and forms an image having excellent scratch resistance and adhesion to the substrate. Examples of glycol ether solvents include glycol ethers and glycol ether acetates. Examples of glycol ethers include diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol dimethyl ether. Etc. Examples of glycol ether acetates include ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of boiling point, one or more selected from diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol dimethyl ether are preferable.

  The content of the glycol ether solvent is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the entire reaction ink. If the content is less than 1 part by weight, the film-forming effect of the emulsion may not be sufficiently obtained. On the other hand, if the content exceeds 40 parts by weight, the amount of volatile organic compound (VOC) emitted may be greater than the regulated value, and may not be preferable from the viewpoint of safety. The content of the glycol ether solvent is more preferably 5 parts by weight or more and more preferably 20 parts by weight or less with respect to 100 parts by weight of the entire reaction ink.

(water)
Examples of water include ion exchange water, distilled water, tap water, and well water. Among these, ion-exchanged water is preferable from the viewpoint of relatively few impurities and being available at low cost.

  If necessary, the reactive ink may contain other additives as long as the effects of the present invention are not impaired. Examples of other additives include antifungal agents, chelating agents, pH adjusters, and rust inhibitors.

  The reaction ink is not particularly limited. For example, the flocculant, the water-soluble organic solvent, the water, and, if necessary, other additives are uniformly mixed using a mixing and stirring device. By doing so, it can be manufactured.

  The reaction ink produced in this manner preferably has a viscosity at 25 ° C. of 1 to 15 mPa · s or less from the viewpoint of improving dischargeability from the inkjet head. The viscosity of the reactive ink can be measured using an R100 type viscometer in accordance with JIS Z 8803.

  The reactive ink preferably has a static surface tension of 15 to 40 mN / m from the viewpoint of improving the wettability with respect to the substrate and improving the suitability of the inkjet head. The static surface tension was measured at 25 ° C. using a fully automatic equilibrium electro surface tension meter ESB-V (manufactured by Kyowa Kagaku).

The reactive ink preferably has a dynamic contact angle of 10 ° or more, and 40 ° or less after 3 seconds from the contact with the fabric, from the viewpoint of sufficiently exhibiting the anti-bleeding effect of the reactive ink. Is preferred. The dynamic contact angle is measured by dropping 1 μL of the reaction ink in a dynamic mode onto a target substrate maintained at 40 ° C. using a portable contact angle meter PG-X (manufactured by Matsubo). did.
<Inkjet printing method>
The inkjet textile printing method according to the present embodiment is a method of forming an image on a fabric using the inkjet ink set according to the present embodiment, wherein the aqueous ink and the reactive ink are brought into contact with the fabric. Simultaneously and almost simultaneously, droplets are ejected from the inkjet head. Thereby, the image excellent in the coating-film characteristic can be formed on the said fabric. Almost simultaneously means that, for example, in a staggered head, the reactive ink is printed from the head arranged in front of the print winding side, and the printed reactive ink is sufficiently dried. Then, it means that aqueous (color) ink is printed from the head disposed on the back side and is contacted on the fabric.

  In the inkjet textile printing method according to the present embodiment, the aqueous ink and the reactive ink are moved from the inkjet head while moving the inkjet head filled with the aqueous ink and the reactive ink to a position relative to the fabric. Is discharged onto the fabric. The water-based ink and the reactive ink may be discharged simultaneously from the inkjet head, or the water-based ink may be discharged after discharging the reactive ink.

  In the inkjet textile printing method according to this embodiment, it is preferable that the water-based ink and the reactive ink are ejected from the inkjet head in a temperature range of 20 to 40 ° C. Moreover, it is preferable that the temperature of the fabric when discharging the water-based ink and the reactive ink is 10 to 50 ° C. Furthermore, it is preferable that the dropping amount per unit area of the reactive ink is 10 to 100% with respect to the dropping amount of the water-based ink.

Although the said fabric is not specifically limited, Arbitrary natural fibers and artificial fibers, such as cotton, silk, hemp, wool, rayon, nylon, polyester, can be used. In particular, effects such as improvement in color development can be expected for highly hydrophobic fabrics such as polyester, acrylic, and nylon.
[Example]
Hereinafter, examples that more specifically disclose the present embodiment will be described. In addition, this invention is not limited only to these Examples. Further, unless otherwise indicated, “part” means “part by weight” in the following.
Example 1
<Water-based (color) ink>
(Preparation of pigment dispersion)
After measuring and blending the pigment dispersion with the following composition, zirconia beads having a bead diameter of 0.3 mm (YTZ ball, manufactured by Nikkato Co., Ltd.) were dispersed for 60 minutes using a paint shaker manufactured by Toyo Seiki Co., Ltd. And pigment dispersion A was obtained.
Pigment: (carbon black pigment, manufactured by Mitsubishi Chemical Corporation, “# 1000”): 15.0 g
Dispersant: (Polyoxyethylene alkyl ether sulfonic acid sodium salt, manufactured by Nippon Emulsifier Co., Ltd., trade name “New Coal 1020-SN”): 5.0 g
Water: 80.0g
Next, after the pigment dispersion A prepared above and the materials shown below were weighed, mixed and stirred with a disper, the prepared ink was filtered through a 0.8 μm glass filter (GFP, manufactured by Kiriyama Seisakusho). Then, an aqueous color ink for ink jet recording (hereinafter referred to as color ink) A was produced.
Pigment dispersion A (pigment concentration: 15%): 20.0 parts Emulsion resin: (Styrene-acrylic, Nippon Synthetic Chemical Co., Ltd., “Movinyl 966A”, resin component 45%): 20.0 parts Silicon-based surface activity Agent: (BYK345, manufactured by Big Chemie): 0.3 part wetting agent (manufactured by Nissin Chemical Industry Co., Ltd., “Orphine E-1004”): 0.5 part preservative (manufactured by Lonza Japan, “PROXEL GXL (S ) "): 0.02 parts 1,3-butylene glycol (manufactured by KH Neochem): 20.0 parts Water: 39.2 parts <Reaction ink>
The materials shown below were weighed, mixed and stirred with a disper, and then the prepared ink was filtered through a 0.8 μm glass filter to prepare inkjet recording reaction ink (hereinafter referred to as reaction ink) A.
Flocculant: (polyallylamine-based, manufactured by Nitto Bo Medical, “PAA-15”) (primary amine): 6.0 parts (2) 1,2-octanediol: (manufactured by Kyoto Wako Pure Chemical Industries, Ltd.): 1. 0 parts (3) Diethylene glycol monobutyl ether: (Nippon Emulsifier, “BDG”): 10.0 parts (4) 1,3-butylene glycol: (KH Neochem): 10.0 parts (5) Preservative ("PROXEL GXL (S)" manufactured by Lonza Japan): 0.02 parts (6) Water: 78.4 parts <Ink set>
Ink set A composed of color ink A and reactive ink A was prepared.
<Printing method>
Using a inkjet printer UJF-3042HG (manufactured by Mimaki Engineering Co., Ltd.) equipped with the prepared ink set A, as a fabric for printing on a stage temperature-controlled at 30 ° C., a multifilament woven fabric for dyeing fastness test (cotton, Nylon, Acetate, Hair, Rayon, Acrylic, Silk, Polyester, Conforming to JIS L-0803), and printing density is set to 50% reactive ink and 100% color ink in this order in a printing mode of resolution 720 x 600 dpi and 8 Pass. A solid image was printed. Then, it dried for 10 minutes in a 60 degreeC thermostat, and produced the printing sample.

(Example 2)
The reaction ink B was prepared using “PAA-03” (primary amine) manufactured by Nitto Bo Medical Co., Ltd. as a reaction ink aggregating agent, and ink set B was prepared in the same manner as in Example 1. A print sample was prepared.

(Example 3)
The reaction ink C was prepared using “PAA-25” (primary amine) manufactured by Nitto Bo Medical Co., Ltd. as a reaction ink aggregating agent, and ink set C was prepared in the same manner as in Example 1. A print sample was prepared.

(Comparative Example 1)
A print sample was prepared in the same manner as in Example 1 except that only the color ink A was used and only the color ink 100% was printed without using the reactive ink.

(Comparative Example 2)
The reaction ink D was prepared using a dimethylamine epichlorohydrin series, “Kachio Master PD-7” (quaternary amine) manufactured by Yokkaichi Gosei Co., Ltd. A print sample was produced in the same manner as in Example 1.

<Evaluation method>
(Reactive ink initial discharge)
The state of nozzle omission when the test ink was filled with the reaction ink and a test drawing pattern was printed was determined according to the following criteria.

○: No more than 2 nozzles △: No more than 3-10 nozzles No: No more than 11 nozzles (Stability of reactive ink)
After the printing test is finished, after leaving for 24 hours at room temperature with the automatic cleaning function of the head filled with reactive ink turned off, the state of nozzle missing when printing the test drawing pattern of reactive ink is as follows: Judgment was made based on the criteria.

○: Nozzle drop was reduced to 2 or less by performing normal cleaning once. Δ: Nozzle drop was reduced to 2 or less by performing normal cleaning three times.

  X: Even if normal cleaning was performed 3 times, 3 or more nozzles which did not discharge were seen.

(Measurement of hue and reflection density)
The printed portion of the print sample is measured using a spectrocolorimeter (X-Rite 939, manufactured by X-Rite), and the reflection density value and hue L * a * b * value at the light source D65 / 10 ° viewing angle. Was measured.

(OD value evaluation with polyester)
Among the print samples, the reflection density value (V value) of the polyester printing surface was determined according to the following criteria.

○: OD value is 1.0 or more ×: OD value is smaller than 1.0 (Evaluation of fastness to washing)
Weighed 1500 g of water and 1.0 g of liquid detergent (trade name “Ultra Attack NEO”, manufactured by Kao Corporation) in a 2 L beaker, taken out with stirring for 10 minutes with a stirrer in a state where a print sample was put, and dried. . The color difference ΔE was determined from the hue L * a * b * of the polyester printed surface before and after drying, and judged according to the following criteria.

○: ΔE is smaller than 3 Δ: ΔE is within 3 to 10 ×: ΔE is larger than 10 Table 1

In Example 1, it was the result excellent in each of discharge property, OD value in the polyester surface, and wash fastness. In Example 2, the example in which the flocculant was not used in the reactive ink was not fixed on the fiber surface from Comparative Example 1, and thus the evaluation of the OD value indicating color developability was x. This is because the water-based ink is printed directly on the fabric, so that the ink easily penetrates into the fabric, and the pigment serving as the colorant hardly stays on the fabric surface.
On the other hand, even when a flocculant was used, in the case of a quaternary amine, the evaluation of the OD value indicating color developability was “good”, but the fastness to washing was “poor”. This is because the reactivity with the emulsion and the pigment in the water-based ink is poor because the reactivity is lower than that of the primary amine, and the fastness to washing is lowered.

  The ink jet textile printing method of the present invention can provide an image having excellent coating properties such as scratch resistance and adhesion.

Claims (9)

An inkjet printing method using a water-based ink and a reactive ink,
The water-based ink includes at least an emulsion, a water-soluble organic solvent, a pigment, and water,
The reactive ink includes a flocculant composed of a water-soluble cationic polymer having a primary amine group, a water-soluble organic solvent, and water.
An ink-jet printing method, wherein a reactive ink is printed on a fabric by ink jet printing on an image forming portion, and at the same time, an aqueous ink is printed on an image forming portion and brought into contact with the fabric.   The inkjet printing method according to claim 1, wherein the water-soluble cationic polymer has a weight average molecular weight of 5,000 to 20,000 as determined by GPC (gel permeation chromatography).   The inkjet printing method according to claim 1 or 2, wherein the water-soluble cationic polymer is polyallylamine or polyvinylamine.   The inkjet printing method according to claim 1, wherein the reactive ink contains 1,2-alkanediol having 7 to 10 carbon atoms.   The inkjet printing method according to claim 1, wherein the reactive ink does not contain a surfactant.   6. The ink-jet printing method according to any one of 1 to 5, wherein the pigment is dispersed by a surfactant.   The ink-jet printing method according to any one of claims 1 to 6, wherein the fabric is polyester alone or a blend of polyester and other fibers.   The inkjet printed matter printed by the method in any one of Claims 1-7. An inkjet ink set having a water-based ink and a reactive ink,
The water-based ink includes at least an emulsion, a water-soluble organic solvent, a pigment, and water. The reaction ink includes a flocculant composed of a water-soluble cationic polymer having at least a primary amine group, and a water-soluble organic solvent. Ink-jet ink set comprising water.