JP2012153754A - Inkjet ink set for textile printing and inkjet textile printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet ink set for textile printing preventing discoloration in a fabric white part during a color developing step and a washing step, and an inkjet textile printing method using the inkjet ink set for textile printing.SOLUTION: The inkjet ink set for textile printing consists of functional ink containing an anticorrosive and recording ink containing a coloring agent. The functional ink contains an alkaline chemical or an acid compound. The anticorrosive is at least one compound selected from organic acids, salts of the organic acids, amines, nitrites, and benzotriazoles.

Description

  The present invention relates to a novel inkjet ink set for textile printing and an inkjet textile printing method using the same, and more specifically, an inkjet ink set composed of a functional ink containing a rust inhibitor and a recording ink containing a colorant. The present invention relates to an ink jet textile printing method for printing on a fabric using the same.

  Conventional textile printing is performed using a printing method using a plate or a screen printing method. On the other hand, a textile printing method using an inkjet method is known. This textile printing method is non-printing, suitable for a small quantity and a wide variety, and has a feature that a printed matter can be produced with a short delivery time.

  When printing on a fabric by an ink jet method, there is a case where bleeding occurs. Usually, the fabric is pretreated for the purpose of preventing bleeding and improving the fixability between the colorant and the fabric. Specifically, after dipping or coating the fabric using a polymer compound for preventing bleeding, an acid or alkali for improving fixability, and an aqueous solution containing urea as a hydrotropic agent as a pretreatment agent A drying process is applied.

  Such a fabric pretreatment step is indispensable for inkjet textile printing, but the current method has various problems as shown below.

1) Time is required for pre-processing, and the delivery time of the print is delayed 2) Cost for the pre-processing step is required 3) The pre-processed fabric deteriorates with time and cannot be stored for a long time On the other hand, a method for pre-processing a fabric in a pre-printing process has been proposed. For example, Patent Document 1 discloses a textile printing method in which a recording ink is applied after applying a functional ink such as a pretreatment agent to a fabric using an inkjet head. In this method, it is preferable to apply functional ink to a white background around the area to which the recording ink is applied in order to prevent bleeding of the recording ink and to ensure that the colorant is stably and firmly fixed to the fabric. It is said that.

  Since functional ink contains alkali and acid, if a metal member is used in the recording ink flow path system, the metal member may corrode. As the metal member corrodes, the metal ions are eluted into the functional ink and applied to the fabric together with the functional ink, so that the white background portion of the fabric may be colored in the subsequent coloring process or washing process. .

  As a method for preventing bleeding of the recording ink and fixing the colorant to the fabric more reliably and stably, the functional ink is applied to the fabric and then dried by heating means mounted on the printer. However, since the functional ink is heated by the heat of the heating means, the corrosion of the metal member is promoted, and the above-mentioned problem of coloring the white background is likely to occur. Also, the method of mounting the heating means on the carriage mounted on the ink jet head is to prevent the recording ink from bleeding and to make the colorant more stable and stable by drying immediately after the functional ink is applied to the fabric. Although effective for fixing to the fabric, the functional ink flow path system and the heating means are close to each other, so that the metal member is more easily corroded by the heating of the functional ink, and the problem of coloring the white background portion is more likely to occur.

  Patent Document 2 describes an example in which benzotriazole, which is a rust preventive agent, is included in a recording ink. However, in such a method, a white background portion of a fabric caused by corrosion of a metal member in a functional ink flow path system is described. The coloring problem cannot be solved. In addition, when a colorant and a rust preventive agent coexist, precipitates are generated in the ink, which may hinder the storage stability and emission stability of the ink.

  Patent Document 3 and Patent Document 4 have a description that precipitates are generated in ink when a benzotriazole-based compound and a copper complex colorant coexist.

JP 2005-232633 A JP-A-2005-47990 JP 2000-355665 A JP 2008-74885 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an inkjet ink set for printing capable of preventing coloring of a white fabric background in a coloring process and a washing process, and an inkjet printing method using the same. It is to provide.

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

  1. An inkjet ink set for textile printing comprising at least a functional ink containing a rust inhibitor and a recording ink containing a colorant.

  2. 2. The inkjet ink set for textile printing according to 1 above, wherein the functional ink contains an alkali agent or an acid compound.

  3. 3. The inkjet ink for textile printing according to 1 or 2, wherein the rust inhibitor is at least one compound selected from organic acids, salts of organic acids, amines, nitrites, and benzotriazoles. set.

  4). The inkjet ink set for textile printing according to any one of 1 to 3, wherein the functional ink contains a rust inhibitor in an amount of 0.1% by mass to 5.0% by mass.

  5). The inkjet ink set for textile printing according to any one of 1 to 4, wherein the functional ink contains 2-imidazolidinone.

  6). 6. An ink jet printing method using the ink jet ink set for textile printing according to any one of 1 to 5, wherein a functional ink is applied to a fabric using an ink jet head, and then a recording ink is applied to the fabric. An ink-jet printing method characterized by the above.

  7). 7. The inkjet printing method according to 6 above, wherein the recording ink is applied to the fabric after drying the functional ink applied to the fabric by heating.

  8). 8. The ink-jet printing method as described in 7 above, wherein the heating means for heating and drying the functional ink is mounted on an ink-jet printer.

  9. 9. The ink-jet printing method as described in 8 above, wherein the heating means for heating and drying the functional ink is mounted on a carriage on which an ink-jet head is mounted.

  According to the present invention, it is possible to provide an inkjet ink set for textile printing that can prevent coloring of a white fabric background part in a coloring process and a washing process, and an inkjet textile printing method using the same.

It is the partial schematic which shows an example of a structure of an inkjet textile printing apparatus. It is the partial schematic diagram which looked at the carriage of the ink jet textile printing device shown in Drawing 1 from the upper part. It is the partial schematic diagram which looked at the carriage of the ink jet textile printing device shown in Drawing 1 from the upper part. It is the partial schematic which shows another example of a structure of an inkjet textile printing apparatus. It is the partial schematic diagram which looked at the carriage of the ink jet textile printing device shown in FIG.

  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 inventor has at least a functional ink containing a rust inhibitor and a recording ink containing a colorant, and an inkjet ink for textile printing, It has been found that by using the set, coloring of the white fabric background in the coloring process and the washing process can be prevented, and the present invention has been completed.

  Hereinafter, the details of the inkjet ink set for textile printing of the present invention and the inkjet textile printing method using the same will be described.

《Inkjet ink set for textile printing》
The inkjet ink set for textile printing of the present invention (hereinafter also simply referred to as ink set) is composed of a functional ink containing a rust preventive agent and a recording ink containing a colorant.

[Functional ink]
The functional ink according to the present invention contains at least a rust inhibitor. In addition, polymer compounds for the purpose of preventing bleeding when recording ink is applied, acids and alkalis for improving the fixing property of colorants, hydrotropic agents, water-soluble organic solvents and other additives as necessary Etc. can be contained.

(Rust inhibitor)
The anticorrosive agent applicable to the functional ink according to the present invention is not particularly limited. For example, 1) a passive film on a metal surface such as nitrite, chromate, molybdate, tungstate, etc. 2) Those that form an insoluble film on the metal surface by binding with Ca ions in the ink such as polymerized phosphates and zinc salts 3) Mercaptobenzothiazoles, benzotriazoles, etc. Examples include those that bind to metal ions on such metal surfaces to form insoluble films, and 4) those that form films by adsorbing on metal surfaces such as amines and organic acids and their salts, etc. In the present invention, it is preferable to use at least one compound selected from organic acids, salts of organic acids, amines, nitrites and benzotriazoles as a rust inhibitor.

  a) Examples of organic acids and salts thereof include the following organic acids and alkali metal salts, ammonium salts, and amine salts thereof.

  Examples of the organic acids include butyric acid, valeric acid, caproic acid, capric acid, caprylic acid, lauric acid, palmitic acid, stearic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, Aliphatic (di) carboxylic acids such as undecanedioic acid, brassic acid, benzoic acid, alkylbenzoic acid, hydroxybenzoic acid, alkoxybenzoic acid, nitrobenzoic acid, aminobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, nitrophthalic acid And aromatic (di) carboxylic acids such as aminophthalic acid, amino acids such as aspartic acid and glutamic acid, citric acid, malic acid, tartaric acid, lactic acid and gluconic acid.

  Examples of the organic acid salts include sodium salts, potassium salts, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, and trimethylamine salts of the above organic acids.

  b) Examples of amines include alkylamines such as methylamine, butylamine, hexylamine, dimethylamine and trimethylamine, alicyclic amines such as cyclohexylamine, ethanolamine, diethanolamine, triethanolamine, and N-methylethanol. Alkanol amines such as amine, isopropanolamine, diisopropanolamine, triisopropanolamine, aromatic amines such as aniline and phenethylamine, cyclic amines such as piperidine, morpholine, and piperazine, alkoxyalkylamines, polyoxyalkylenealkylamines, etc. Ether amine, ethylenediamine, diamine such as hexamethylenediamine, cationic amine such as alkylamine salt, quaternary ammonium salt, alkylbeta Emissions, such amphoteric surfactant such as an alkyl amine oxide.

  c) Examples of nitrites include sodium nitrite, potassium nitrite, ammonium nitrite and the like.

  d) Examples of benzotriazoles include benzotriazole, tolyltriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5' -Methylphenyl) benzotriazole and the like.

  In the functional ink according to the present invention, the content of the rust inhibitor is preferably in the range of 0.1 to 5.0% by mass with respect to the total mass of the functional ink. When the content of the rust inhibitor is less than 0.1% by mass, it becomes difficult to obtain the object effect of the present invention. It is disadvantageous in terms.

(Alkaline agent)
The functional ink according to the present invention can contain an alkali agent. This is particularly preferred when the recording ink uses a reactive dye as a colorant.

  The alkaline agent applicable to the present invention can be selected from organic bases and inorganic bases, but water-soluble inorganic bases are preferable in terms of color development, odor, solubility in recording ink, drainage load, and the like. . Examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, ammonium acetate, lithium acetate, acetic acid. Examples thereof include sodium, potassium acetate, and sodium triphosphate.

  In the case where the functional ink is applied to the fabric using an inkjet method, it is preferable to use a potassium salt as the alkaline agent because precipitation with the functional ink hardly occurs and ejection from the inkjet head is stable.

  The content of the alkali agent in the functional ink according to the present invention is preferably 1.0 to 10% by mass with respect to the total mass of the functional ink.

(Acid compound)
The functional ink according to the present invention can contain an acid compound. This is particularly preferred when the recording ink uses an acid dye, a disperse dye and a pigment as a colorant.

  The acid compound can be selected from various inorganic acids and organic acids.

  Examples of the inorganic acid include acetic acid, hydrochloric acid, sulfuric acid, chlorous acid, nitric acid, nitrous acid, sulfurous acid, phosphorous acid, phosphoric acid, chloric acid, and hypophosphorous acid.

  Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, Tricarballylic acid, glycolic acid, thioglycolic acid, lactic acid, malic acid, tartaric acid, citric acid, isocitric acid, gluconic acid, pyruvic acid, oxalacetic acid, diglycolic acid, benzoic acid, phthalic acid, mandelic acid, salicylic acid, etc. Among these, tartaric acid, citric acid and malic acid are preferably selected.

  In addition, acid ammonium salts such as ammonium sulfate and ammonium tartrate, which generate an acid in a subsequent step, are also preferably used.

  The content of the acid compound is preferably 1.0 to 10% by mass with respect to the total mass of the functional ink.

(Polymer compound)
The functional ink according to the present invention can contain a polymer compound. Examples of the polymer compound include natural gums such as guar gum and locust bean gum, starches, seaweeds such as sodium alginate, funari, plant skins such as pectic acid, cellulose such as methylcellulose, ethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose. Derivatives, roasted starch, alpha starch, carboxymethyl starch, carboxyethyl starch, hydroxyethyl starch and other modified starches, processed natural gum, roast bean gum and other processed natural gums, algin derivatives, or polyvinyl alcohol, polyacrylate Synthetic glues such as, emulsions and the like can be used.

  When a functional ink is applied on a fabric using an inkjet method, the polymer compound is polyvinyl pyrrolidone, polyethylene glycol, ethylene oxide propylene oxide copolymer, polyethylene oxide adduct of glycerin, polypropylene adduct of glycerin, diglycerin. It is preferable to use a polyethylene oxide adduct of diglycerin and a polypropylene adduct of diglycerin.

  The content of the polymer compound in the functional ink is preferably 1.0 to 10% by mass.

(Hydrotropy)
The functional ink according to the present invention may contain a hydrotropic agent. Examples of the hydrotropic agent include water-soluble amides, sulfonamides, urea and derivatives thereof, 2-imidazolidinone and derivatives thereof, and it is preferable to use 2-imidazolidinone and derivatives thereof. . Since 2-imidazolidinone and its derivatives are not hydrolyzed like urea, for example, the storage stability and the emission stability of the functional ink are not deteriorated.

  Examples of 2-imidazolidinone and its derivatives include 2-imidazolidinone, 1-methyl-2-imidazolidinone, 1-ethyl-2-imidazolidinone, 1,1′-dimethyl-2-imidazolidi Non, 1,3-dimethyl-2-imidazolidinone, 1,1'-diethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone 4,5-dimethyl-2-imidazolidinone, 4,5-diethyl-2-imidazolidinone, 1-tert-butyl-2-imidazolidinone, 4,5-dimethoxy-2-imidazolidinone, 4, , 5-diethoxy-2-imidazolidinone, 1,3-dimethyl-4,5-dimethoxy-2-imidazolidinone, 1,3-dimethyl-4,5-diethoxy-2-imidazolidino 1- (2-hydroxyethyl) -2-imidazolidinone, 4- (2-hydroxyethyl) -2-imidazolidinone, 4,5-di (2-hydroxyethyl) -2-imidazolidinone, -Acetyl-2-imidazolidinone and the like are mentioned, among which 2-imidazolidinone is preferably used.

  The content of the hydrotropic agent in the functional ink is preferably 5.0 to 30% by mass.

(Water-soluble organic solvent)
The functional ink according to the present invention preferably contains a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, Ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), glycol ethers (eg, ethylene glycol alkyl ether, diethylene glycol alkyl ether) , Triethylene glycol alkyl ether, propylene glycol alkyl ether, dipropy Glycol glycol ether, tripropylene glycol alkyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, trimethylamine) Ethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidino Etc.), sulfoxides (e.g., dimethyl sulfoxide) and the like.

  The content of the water-soluble organic solvent is preferably 5.0 to 40% by mass with respect to the total mass of the functional ink.

(Surfactant)
The functional ink according to the present invention can contain a surfactant. As the surfactant, any type of cationic, anionic, amphoteric, and nonionic surfactants can be used.

  Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.

  Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl-β-alanine salt, N-acyl glutamate, alkyl ether carboxylate, acyl Peptide, alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol Sulfate ester, secondary higher alcohol sulfate, alkyl ether sulfate, secondary higher alcohol ethoxy sulfate, polyoxyethylene alkylphenyl ether sulfate, monoglyculate, fatty acid alkylolamide sulfate, alkyl ether phosphorus acid Examples thereof include ester salts and alkyl phosphate ester salts.

  Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkyl phenyl ether (for example, Emulgen 911, manufactured by Kao Corporation), polyoxyethylene sterol ether, polyoxy Ethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether (for example, Newpol PE-62, manufactured by Sanyo Chemical Industries), polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Esters, polyoxyethylene sorbitol fatty acid esters, polyethylene glycol fatty acid esters, fatty acid monoglycerides, polyglycerin fatty acid esters, sorbitan fatty acid esters , Propylene glycol fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkyl amine oxides, acetylene glycol, acetylene alcohol, and the like.

  When these surfactants are used, they can be used alone or in combination of two or more, and can be added in the range of 0.001 to 1.0% by mass with respect to the total mass of the functional ink.

(Reduction inhibitor)
The functional ink according to the present invention can contain a reduction inhibitor. As the reduction inhibitor, nitrobenzene sulfonate is preferably used, and an alkali metal salt of metanitrobenzene sulfonic acid, particularly a sodium salt is preferably used.

  The content of the reduction inhibitor is preferably 0.1 to 7.0% by mass with respect to the total mass of the functional ink.

(Other additives)
An antiseptic and an antifungal agent can be added to the functional ink according to the present invention. Examples of the antiseptic and antifungal agent include aromatic halogen compounds (for example, Preventol CMK, manufactured by Bayer), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazolin-3-one (for example, PROXEL GXL, manufactured by Avicia).

(Deaerating functional ink)
When the functional ink according to the present invention is applied to a fabric using an ink jet method, if dissolved gas is contained in the functional ink, fine bubbles are formed in the functional ink when ejected from the ink jet head. This is a factor that causes ejection failure. Therefore, it is preferable to remove such dissolved gas from the functional ink. The degassing method is roughly divided into a method of degassing by a physical method such as boiling or pressure reduction, and a function of the absorbent. There is a chemical method of adding and mixing in ink.

  In the present invention, it is possible to perform deaeration by any means, but in particular, functional ink is passed through the hollow fiber membrane having gas permeability, and the outer surface side of the hollow fiber membrane is decompressed. Thus, the method of permeating and removing the dissolved gas in the functional ink is preferable because the dissolved gas in the functional ink can be efficiently removed without adversely affecting the physical properties of the functional ink.

(Applying functional ink)
In the present invention, the functional ink according to the present invention is applied to a fabric using an inkjet head. In this case, it is preferable that an ink jet head for applying the functional ink is mounted on the printer and applied to the fabric online with the recording ink containing the colorant.

  Specifically, (1) functional ink is applied to the fabric, (2) the applied functional ink is dried, and (3) recording ink is applied to form an image. It is preferable to use an ink jet recording apparatus having a configuration that can be completed in the printer.

When applying the functional ink which concerns on this invention to a fabric using an inkjet system, it is preferable that the viscosity of a functional ink is 3-20 mPa * s. The surface tension is preferably 25 to 70 mN / m. The viscosity and surface tension can be adjusted with the above-mentioned polymer compound, water-soluble organic solvent and surfactant, and the amount of functional ink applied to the fabric is 5 to 20 ml / m ^2. Is preferred.

[Recording ink]
Next, the recording ink constituting the inkjet ink set for textile printing according to the present invention will be described.

  The recording ink according to the present invention contains at least a colorant, and may contain a water-soluble organic solvent and other additives as necessary.

(Colorant)
Examples of the colorant applicable to the recording ink according to the present invention include disperse dyes, reactive dyes, acid dyes, direct dyes, pigments, oil-soluble dyes, among others, disperse dyes, reactive dyes, and the like. It is preferable to use a functional dye, an acid dye or a pigment.

  Specific compounds of the colorant that are preferably used in the present invention are shown below, but the present invention is not limited to these exemplified compounds.

<Disperse dye>
As a disperse dye preferably used in the recording ink according to the present invention,
C. I. Disperse Yellow; 3, 4, 5, 7, 9, 13, 23, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 116, 118, 119, 122, 124, 126, 135 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224 227, 231, 232,
C. I. Disperse Orange; 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130 139, 142,
C. I. Disperse Red; 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184 , 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 22 5, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 298, 302, 303, 310, 311, 312, 320, 324, 328,
C. I. Disperse Violet; 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63 69, 77,
C. I. Disperse Green; 9,
C. I. Disperse Brown; 1, 2, 4, 9, 13, 19,
C. I. Disperse Blue; 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143 146, 148, 149, 153, 154, 158, 165, 167, 167: 1, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205 , 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 29 3, 295, 297, 301, 315, 330, 333,
C. I. Disperse Black 1, 3, 10, 24,
Etc.

  In the ink-jet printing method using disperse dyes, when developing colors at high temperatures, disperse dyes on the white background of machines and fabrics will not cause contamination, so select disperse dyes with good sublimation fastness. It is preferable.

<Reactive dyestuff>
As a reactive dye preferably used in the recording ink according to the present invention,
C. I. Reactive Yellow; 2, 3, 7, 15, 17, 18, 22, 23, 24, 25, 27, 37, 39, 42, 57, 69, 76, 81, 84, 85, 86, 87, 92, 95 , 102, 105, 111, 125, 135, 136, 137, 142, 143, 145, 151, 160, 161, 165, 167, 168, 175, 176,
C. I. Reactive Orange; 1, 4, 5, 7, 11, 12, 13, 15, 16, 20, 30, 35, 56, 64, 67, 69, 70, 72, 74, 82, 84, 86, 87, 91 , 92, 93, 95, 107,
C. I. Reactive Red; 2, 3, 3: 1, 5, 8, 11, 21, 22, 23, 24, 28, 29, 31, 33, 35, 43, 45, 49, 55, 56, 58, 65, 66 78, 83, 84, 106, 111, 112, 113, 114, 116, 120, 123, 124, 128, 130, 136, 141, 147, 158, 159, 171, 174, 180, 183, 184, 187 , 190, 193, 194, 195, 198, 218, 220, 222, 223, 226, 228, 235,
C. I. Reactive Violet; 1, 2, 4, 5, 6, 22, 23, 33, 36, 38,
C. I. Reactive Blue; 2, 3, 4, 7, 13, 14, 15, 19, 21, 25, 27, 28, 29, 38, 39, 41, 49, 50, 52, 63, 69, 71, 72, 77 79, 89, 104, 109, 112, 113, 114, 116, 119, 120, 122, 137, 140, 143, 147, 160, 161, 162, 163, 168, 171, 176, 182, 184, 191 , 194, 195, 198, 203, 204, 207, 209, 211, 214, 220, 221, 222, 231, 235, 236,
C. I. Reactive Green; 8, 12, 15, 19, 21,
C. I. Reactive Brown; 2, 7, 9, 10, 11, 17, 18, 19, 21, 23, 31, 37, 43, 46,
C. I. Reactive Black 5, 8, 13, 14, 31, 34, 39,
Etc.

<Acid dye>
As an acid dye preferably used for the recording ink according to the present invention,
C. I. Acid Yellow; 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40: 1, 42, 44, 49, 59, 59: 1, 61, 65, 67, 72, 73 79, 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219: 1, 220, 230, 232, 235, 241, 242, 246,
C. I. Acid Orange; 3, 7, 8, 10, 19, 22, 24, 51, 51S, 56, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127 140, 142, 144, 149, 152, 156, 162, 166, 168,
C. I. Acid Red; 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97: 1, 106, 111, 114, 118, 119, 127 131, 138, 143, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277 289, 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415,
C. I. Acid Violet; 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126,
C. I. Acid Blue; 1, 7, 9, 15, 23, 25, 40, 61: 1, 62, 72, 74, 80, 83, 90, 92, 103, 104, 112, 113, 114, 120, 127, 127 : 1, 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230 239, 258, 260, 264, 277: 1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350,
C. I. Acid Green; 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 56, 73, 81, 84, 104, 108, 109,
C. I. Acid Brown; 2, 4, 13, 14, 19, 28, 44, 123, 224, 226, 227, 248, 282, 283, 289, 294, 297, 298, 301, 355, 357, 413,
C. I. Acid Black; 1, 2, 3, 24, 24: 1, 26, 31, 50, 52, 52: 1, 58, 60, 63, 63S, 107, 109, 112, 119, 132, 140, 155, 172 187, 188, 194, 207, 222,
<Direct dye>
As a direct dye preferably used for the recording ink according to the present invention,
C. I. Direct Yellow; 8, 9, 10, 11, 12, 22, 27, 28, 39, 44, 50, 58, 86, 87, 98, 105, 106, 130, 137, 142, 147, 153,
C. I. Direct Orange; 6, 26, 27, 34, 39, 40, 46, 102, 105, 107, 118,
C. I. Direct Red; 2, 4, 9, 23, 24, 31, 54, 62, 69, 79, 80, 81, 83, 84, 89, 95, 212, 224, 225, 226, 227, 239, 242, 243 254,
C. I. Direct Violet; 9, 35, 51, 66, 94, 95,
C. I. Direct Blue; 1, 15, 71, 76, 77, 78, 80, 86, 87, 90, 98, 106, 108, 160, 168, 189, 192, 193, 199, 200, 201, 202, 203, 218 225, 229, 237, 244, 248, 251, 270, 273, 274, 290, 291,
C. I. Direct Green; 26, 28, 59, 80, 85,
C. I. Direct Brown; 44, 44: 1, 106, 115, 195, 209, 210, 212: 1, 222, 223,
C. I. Direct Black; 17, 19, 22, 32, 51, 62, 108, 112, 113, 117, 118, 132, 146, 154, 159, 169,
<Pigment>
As a pigment preferably used in the recording ink according to the present invention,
Carbon black,
C. I. Pigment Yellow; 1, 3, 12, 13, 14, 16, 17, 43, 55, 74, 81, 83, 109, 110, 120, 138, 150,
C. I. Pigment Orange; 13, 16, 34, 43,
C. I. Pigment Red; 2, 5, 8, 12, 17, 22, 23, 41, 112, 114, 122, 123, 146, 148, 149, 150, 166, 170, 220, 238, 245, 258,
C. I. Pigment Violet; 19, 23,
C. I. Pigment Blue; 15, 15: 1, 15: 3, 15: 4, 15: 5, 15: 6, 29,
C. I. Pigment Brown 22,
C. I. Pigment Black; 1, 7,
C. I. Pigment White 6,
Etc.

  In the present invention, the content of the colorant contained in the recording ink is preferably from 0.1 to 20 mass%, more preferably from 0.2 to 13 mass%, based on the total mass of the recording ink.

(Water-soluble organic solvent)
As the water-soluble organic solvent used in the recording ink according to the present invention, the same water-soluble organic solvents as those used in the above-described functional ink can be used. The content of the water-soluble organic solvent is preferably 10 to 60% by mass with respect to the total mass of the recording ink.

(Surfactant)
As the surfactant used in the recording ink according to the present invention, the same surfactants as those used in the functional ink described above can be used.

  When these surfactants are used, they can be used alone or in combination of two or more, and by adding in a range of 0.001 to 1.0% by mass with respect to the total mass of the recording ink, The surface tension can be arbitrarily adjusted, which is preferable.

(Inorganic salt)
In the recording ink according to the present invention, an inorganic salt can be added to the ink in order to keep the ink viscosity and the dye stable and improve the color development.

  Examples of the inorganic salt include sodium chloride, sodium sulfate, magnesium chloride, magnesium sulfate and the like. The present invention is not limited to these.

(Fixing resin)
In the recording ink according to the present invention, when a pigment is used as the colorant, a fixing resin for fixing the pigment to the cloth can be contained.

  The fixing resin applicable to the present invention may be an ink-soluble resin or an ink-dispersible resin, and it is also preferable to use both in combination. When used together, it is preferable to contain 2 to 10% by mass of the ink-soluble resin and 1 to 10% by mass of the ink dispersible resin, and the total amount is 2 to 15% by mass of the total mass of the recording ink. .

  The ink-soluble resin is preferably a resin having a solubility of about 10% by mass with respect to at least the recording ink vehicle. The ink-soluble resin has a function as a binder resin for improving the durability of the image, so it is stably dissolved in the recording ink, but it is given water resistance after being applied to the fabric and dried. It is preferable that it is resin made.

  As such a resin, a resin having a hydrophobic component and a hydrophilic component in a predetermined balance is designed and used. In this case, the hydrophilic component may be either ionic or nonionic, more preferably ionic, and still more preferably anionic. In particular, those that are rendered water-soluble by neutralizing anionic substances with a volatile base component are preferred.

  The fixing resin that can be particularly preferably used in the present invention is a water-soluble copolymer obtained by neutralizing and dissolving a polymer obtained by polymerizing an unsaturated vinyl having a carboxyl group or a sulfonic acid group as a monomer component with amines, A resin having an acid value of 80 to 300 mgKOH / g is preferred.

  Examples of such resins include acrylic resins, styrene-acrylic resins, acrylonitrile-acrylic resins, vinyl acetate-acrylic resins, polyurethane resins, and polyester resins.

  As the ink-soluble resin preferably used in the present invention, a resin obtained by copolymerizing a hydrophobic monomer and a hydrophilic monomer can be used.

  Examples of the hydrophobic monomer include acrylic acid esters (for example, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc.), methacrylic acid esters (for example, ethyl methacrylate, butyl methacrylate, methacrylic acid). Glycidyl acid), styrene and the like.

  Examples of the hydrophilic monomer include acrylic acid, methacrylic acid, acrylamide and the like. What has an acidic group like acrylic acid can use preferably the thing neutralized with the base after superposition | polymerization.

  The acidic group such as a carboxyl group that the ink-soluble resin has is preferably neutralized partially or completely with a base component. As the neutralizing base in this case, an alkali metal-containing base such as sodium hydroxide or potassium hydroxide, or an amine can be used. In particular, an embodiment in which neutralization with amines is preferable, such as ammonia, triethylamine, 2-dimethylaminoethanol, 2-di-n-butylaminoethanol, methyldiethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, Triethanolamine, 2-methylaminoethanol and the like can be preferably used.

  In particular, neutralization with amines having a boiling point of less than 200 ° C. is more preferable because amines are likely to volatilize during drying, and the hydrophobicity is increased rapidly to contribute to improvement in image durability.

  In the present invention, the content of the water-soluble copolymer is preferably 1.0 to 10% by mass and more preferably 2.0 to 10% by mass with respect to the total mass of the recording ink. In particular, when the content is 2.0% by mass or more, the degree of thickening during drying is sufficient, and bleeding can be prevented and a high-quality image can be obtained. If the amount is 10% by mass or less, the storage stability of the ink is high, and the ink can be stably ejected, and a print can be obtained stably over a long period of time.

  The ink-soluble resin having an acidic group that is preferably used in the present invention preferably has an acid value of 80 mgKOH / g or more and less than 300 mgKOH / g. This increases the viscosity of the resin during drying. In addition to being noticeable, it solidifies firmly even after drying, and the fixing property of the colorant is improved. A more preferable acid value is 90 mgKOH / g or more and less than 250 mgKOH / g. The acid value as used in the present invention can be measured according to JIS K0070.

  The polymerization method of the ink-soluble resin is preferably solution polymerization. The molecular weight of the ink-soluble resin is preferably 3000 to 30000, more preferably 7000 to 20000 in terms of average molecular weight.

  Furthermore, the Tg of the ink-soluble resin is preferably about −30 ° C. to 100 ° C., more preferably −10 ° C. to 80 ° C.

  As the ink dispersible resin, a dispersion polymerized in an aqueous system may be used as it is or may be treated, or a polymer polymerized in a solvent system may be dispersed in an aqueous system. It can be selected from urethane, styrene, vinyl acetate, vinylidene chloride, vinyl chloride, styrene-butadiene, styrene-acrylonitrile, polybutadiene, polyethylene, polyisobutylene, polyester, and the like.

  As a physical property of the recording ink, it is preferable that there is no shear dependency on the viscosity. From this viewpoint, the dispersion form of the polymer fine particles is made to have a low concentration of an emulsifier such as an active agent, or a soap-free aqueous dispersion type using no emulsifier. Polymer fine particles are preferred.

  A preferred aqueous dispersion polymer fine particle is a self-dispersion dispersion of a copolymer obtained by polymerizing unsaturated vinyl having a carboxyl group as at least a monomer component. For example, an acrylic monomer such as ethyl acrylate alone or an acrylic monomer is used. Mechanical dispersion is obtained by swelling a dispersion obtained by emulsion polymerization or suspension polymerization of acrylic acid or maleic acid as a carboxylic acid monomer into a composition comprising an ethylenically unsaturated monomer that can be copolymerized with a monomer, and then mechanically shearing. Is an acrylic hydrosol obtained by dividing the particles. Among acrylic hydrosols, it is preferable to contain styrene in the monomer composition from the viewpoint of increasing the refractive index of the resin and obtaining a high gloss feeling.

  Examples of the alkali include ammonia, triethylamine, 2-dimethylaminoethanol, 2-di-n-butylaminoethanol, methyldiethanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, triethanolamine, 2- An amine such as methylaminoethanol is preferable, and ammonia, 2-amino-2-methyl-1-propanol, and 2-methylaminoethanol are preferably used in terms of dispersion stability of the aqueous dispersion polymer fine particles.

  As the acrylic hydrosol, for example, John Crill manufactured by Johnson Polymer Co., Ltd. is commercially available.

  The glass transition temperature (Tg) of the aqueous dispersion polymer fine particles is preferably 35 ° C. or higher from the viewpoint of improving the scratch resistance of the image, and more preferably 49 ° C. or higher. Although the upper limit of Tg is not particularly limited, a flexible ink film can be obtained when the temperature is generally less than 100 ° C., and cracking failure of an image due to bending of a printed matter can be prevented. The acid value of the water-based dispersed polymer fine particles is preferably 44 mgKOH / g or more, more preferably 60 mgKOH / g or more from the viewpoint of obtaining good redispersion / solubility of the ink dry film. The upper limit of the acid value is not particularly limited, but is preferably less than 110 mgKOH / g from the viewpoint of easily obtaining a more stable dispersion.

  The average particle size of the water-dispersed polymer fine particles is preferably 300 nm or less, more preferably 130 nm or less, from the viewpoint that there is no clogging in the nozzle of the inkjet head and a good gloss feeling is obtained. The lower limit of the average particle diameter is preferably 30 nm or more from the viewpoint of the production stability of the fine particles. The average particle diameter of the water-dispersed polymer fine particles can be easily measured using a commercially available measuring device using a light scattering method or a laser Doppler method. Alternatively, the dispersion of the aqueous dispersion polymer fine particles can be freeze-dried, and the average particle diameter can be converted from the particles observed with a transmission microscope. The content of the ink dispersible resin is preferably 1 to 10% by mass with respect to the total amount of ink.

(Other additives)
In the recording ink according to the present invention, an antiseptic and an antifungal agent can be added to the ink in order to maintain the long-term storage stability of the ink. Examples of the antiseptic and antifungal agent include aromatic halogen compounds (for example, Preventol CMK, manufactured by Bayer), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazolin-3-one (for example, PROXEL GXL, manufactured by Avicia). The present invention is not limited to these.

(Dispersion of colorant)
In the recording ink according to the present invention, when a disperse dye or pigment is used as the colorant, the colorant, the dispersant, the wetting agent, the medium, and any additive are mixed and then dispersed into fine particles using a disperser. be able to. As the disperser, conventionally known dispersing means such as a ball mill, a sand mill, a line mill, a high-pressure homogenizer, and the like can be used.

  The average particle size of the disperse dye or pigment is preferably 300 nm or less as the average particle size and 900 nm or less as the maximum particle size. This is because if the average particle size or the maximum particle size exceeds the range specified above, clogging is likely to occur in an ink jet printing method in which light is emitted from a fine nozzle, and stable emission cannot be performed. The average particle diameter can be determined by a commercially available particle size measuring instrument using a light scattering method, an electrophoresis method, a laser Doppler method or the like. Specific examples of the particle size measuring device include Zetar Sizer Nano-S90 manufactured by Malvern.

  Dispersants preferably used in the ink according to the present invention include, for example, a formalin condensate of sodium creosote oil sulfonate (eg, Demol C, manufactured by Kao Corporation), sodium cresol sulfonate and sodium 2-naphthol-6-sulfonate. Formalin condensate, formalin condensate of sodium cresol sulfonate, formalin condensate of sodium phenol sulfonate, formalin condensate of sodium β-naphthol sulfonate, sodium β-naphthalene sulfonate (eg, Demol N, manufactured by Kao Corporation) And β-naphtholsulfonate sodium formalin condensate, lignin sulfonate (eg, Vanillex RN, Nippon Paper Chemical Co., Ltd.), sodium paraffinsulfonate (eg, Efcol 214, Matsumoto Yushi Seiyaku Co., Ltd.), α-ole Copolymer of fin and maleic anhydride (e.g., Flowlen G-700, manufactured by Kyoeisha Chemical Co., Ltd.), an acrylic polymer active agent (e.g., Joncryl series, BASF Corp.) and the like.

  The amount of the dispersant used is preferably 20 to 200% by mass with respect to the colorant. If the amount of the dispersant is small, it is difficult to make fine particles, and the dispersion stability is also lowered. If the amount of the dispersant is too large, the formation of fine particles and the dispersion stability is inferior, and the viscosity becomes high. These dispersants may be used alone or in combination.

  In the present invention, preferable wetting agents for dispersing the colorant include, for example, sodium dodecylbenzenesulfonate, sodium 2-ethylhexylsulfosuccinate, sodium alkylnaphthalenesulfonate, ethylene oxide adduct of phenol, ethylene oxide addition of acetylenic diol. It is a thing.

  Depending on the structure of the colorant used, foaming, gelation, and fluidity may be deteriorated during dispersion. Therefore, the choice of the dispersing agent and wetting agent depends on the wetting ability, atomization ability, and dispersion stability. In addition, it is necessary to select in consideration of foamability at the time of dispersion, gelation of the dispersion, fluidity of the dispersion, and the like. Dispersants and wetting agents affect the dyeability, dyeing rate, leveling, transferability, color tone, fastness, etc. of the fabric, and when developing at high temperatures, It is preferable to select in consideration of non-uniform dyeing due to tarring of the agent. Since there is no dispersant that satisfies all of the above requirements, it is necessary to select an optimal dispersant according to the colorant to be dispersed and to add an antifoaming agent or the like as necessary.

<< Fabric >>
In the present invention, the material constituting the fabric used in the ink jet textile printing method is not particularly limited as long as it contains fibers that can be dyed with a colorant. Among them, cotton, silk, hemp, wool, nylon It is preferably at least one selected from fibers, rayon fibers, acetate fibers, polyester fibers and blends thereof. As the fabric, the above-described fibers may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric. Further, as the fabric that can be used in the present invention, it is preferable that the fiber that can be dyed with a colorant is 100%. However, a blended woven fabric or a blended nonwoven fabric can also be used as a fabric for printing. . Moreover, as a thickness of the thread | yarn which comprises the above fabrics, the range of 10-100d is preferable.

  In the present invention, in order to obtain a uniform dyed product, natural impurities (oils, waxes, pectic substances, natural pigments, etc.) adhering to the fabric fibers, residues of chemicals used in the fabric production process (such as glue), dirt It is desirable to wash the etc. in advance. Examples of the cleaning agent used for cleaning include alkalis such as sodium hydroxide and sodium carbonate, surfactants such as anionic surfactants and nonionic surfactants, enzymes, and the like.

<Inkjet printing method>
In the ink jet textile printing method for printing on the fabric of the present invention, it is desirable that after printing the ink, the printed fabric is wound up, colored by heating (coloring step), and the fabric is washed and dried. In the ink-jet textile printing method, after ink is printed on a fabric, it is not dyed well just by leaving it alone. In addition, when printing on a long fabric for a long time, the fabric comes out endlessly, and the fabric printed on the floor or the like occupies a place, and it is unsafe and unexpectedly dirty. May end up. Therefore, it is necessary to take up the fabric after printing. At the time of this operation, a method in which a medium such as paper, cloth, vinyl film or the like that is not related to printing can be sandwiched between the cloths. However, when cutting in the middle or when using a short fabric, it is not always necessary to wind up.

  The color development step in the ink jet textile printing method is a method in which the colorant in the ink that has not been sufficiently adsorbed and fixed to the fabric after adhering to the surface of the fabric is reliably adsorbed or fixed to the fabric. This is a step of developing the original hue of the ink. As the method, steaming by steam, baking by dry heat, thermosol, HT steamer by superheated steam, HP steamer by pressurized steam, etc. are used. They are appropriately selected depending on the material to be printed, ink, and the like. Further, the printed fabric may be immediately heat-treated, or may be heat-treated after a while, and may be dried / colored according to the application, and any method may be used in the present invention.

  In the ink jet textile printing method of the present invention, when dyeing with a disperse dye, not only a method of developing a color at a high temperature but also a carrier may be used. The compound used as a carrier is a compound having features such as large dyeing acceleration, simple usage, stable, low impact on human body and environment, easy removal from fibers, and no influence on dye fastness Is preferably used. Examples of the carrier include phenols such as o-phenylphenol, p-phenylphenol, methylnaphthalene, alkyl benzoate, alkyl salicylate, chlorobenzene and diphenyl, ethers, organic acids, hydrocarbons and the like. These have the effect of accelerating the swelling and plasticization of difficult-to-dye fibers that are difficult to dye at temperatures around 100 ° C., such as polyester, and making it easier for disperse dyes to enter the fibers. The carrier may be adsorbed in advance on the fibers of the fabric used for inkjet printing, or may be contained in the functional ink or recording ink.

  When a dye is used as the colorant, a washing step is necessary after the heat treatment. This is because a dye that has not been involved in dyeing remains, so that the color stability is deteriorated and the fastness is lowered. It is also necessary to remove the functional ink applied to the fabric. If left as it is, not only the fastness is lowered, but also the fabric is discolored. Therefore, cleaning according to the object to be removed and the purpose is essential. The method is selected according to the material and ink to be printed. For example, in the case of polyester, a method of treating with a mixed solution of caustic soda, surfactant and hydrosulfite is generally used. This method is usually performed in a continuous type such as an open soaper or a batch type using a liquid dyeing machine, and any method may be used in the present invention.

  After washing, drying is necessary. After the washed fabric is squeezed or dehydrated, it is dried or dried using a dryer, heat roll, iron or the like. Infrared heaters can also be used.

<Inkjet printing device>
An example of an inkjet printing apparatus applicable to the inkjet printing method of the present invention will be described.

(Inkjet head)
In the inkjet textile printing method of the present invention, the functional ink can be applied onto the fabric using an inkjet head (hereinafter also simply referred to as a head). By applying the functional ink with the head, it is possible to uniformly apply the required amount to the required site without unevenness.

  The head used for applying the functional ink to the fabric can be mounted on a carriage different from the carriage on which the head for applying the recording ink is mounted, or can be mounted on the same carriage. When a head for applying functional ink is mounted on a separate carriage, a drying device for drying the functional ink applied to the fabric may be provided after the functional ink is applied and before the recording ink is applied. preferable. Further, when the head for applying functional ink and the head for applying recording ink are mounted on the same carriage, it is preferable to mount the drying device on the carriage.

  The head used for ejecting the functional ink and the recording ink can be selected from various methods such as a piezo method, a thermal method, and a continuous method. The piezo method and the continuous method are preferable because they are highly likely to be stably ejected even with an ink containing a polymer material. In particular, the piezo method is preferable because of its small size and high integration.

(Drying means)
The ink jet textile printing apparatus applicable to the present invention preferably has a drying means for drying the fabric after functional ink is applied to the fabric.

  In the present invention, in the functional ink drying step, it is preferable that the functional ink is dried to the extent that the function of the applied functional ink is expressed to the maximum. In many cases, application of functional ink increases the total amount of ink in combination with subsequent recording ink recording, thereby facilitating bleeding. Therefore, the functionality applied to the fabric is as much as possible. It is preferable to remove ink moisture and organic solvent by drying before applying the recording ink. In the present invention, it is preferable to set the temperature suitable for each composition of the fabric and the functional ink within the range of the surface temperature of the fabric of 30 ° C to 80 ° C.

  In the above drying process, if moisture or organic solvent retained by the functional ink is filled inside the printer, not only will the drying speed be reduced, but the electrical system such as the sensor inside the printer may be corroded. Therefore, it is preferable to sequentially discharge these volatile components to the outside of the printer. For example, it is preferable to apply a method of providing an exhaust tower and forcibly exhausting using a fan or the like.

  Specific methods of drying means applicable to the inkjet printing apparatus used in the present invention include temperature-controllable air or drying means using hot air, drying means using a hot plate, visible light or far-infrared light. The drying means used, the drying means using a heat roller, the drying means using a means for irradiating microwaves, etc. can be appropriately selected and used.

(Configuration of inkjet printing apparatus)
Hereinafter, the specific configuration of the ink jet textile printing apparatus applicable to the present invention described above will be described with reference to the drawings. However, the present invention is not limited only to the configuration exemplified.

  FIG. 1 is a partial schematic diagram illustrating an example of the configuration of an inkjet textile printing apparatus.

  FIG. 1 shows an adhesive belt of an ink jet textile printing apparatus, a roller 3 for driving the adhesive belt, a carriage equipped with an ink jet head 5A for applying functional ink, and a cloth after applying functional ink to the cloth. Only drying means 6A for drying, carriage 5B equipped with an ink jet head for applying recording ink to the cloth, and drying means 6B for drying the cloth after applying the recording ink to the cloth are shown, which are used in the present invention. In addition, the ink jet textile printing apparatus includes control means for applying functional ink and recording ink.

  In FIG. 1, an adhesive belt 1 is an adhesive belt that is held by a support roll 2 and a transport roll 3 and has an adhesive means, particularly preferably a base paste, on an endless substrate belt.

  The fabric P conveyed from the right direction is sandwiched between the nip roll 4 and the adhesive belt 1 and fixed to the adhesive belt 1. Next, the functional ink is applied to the fabric from the functional ink discharge head mounted on the carriage 5A, and then the temperature-controllable wind or warm air is blown. The fan 7A and the heating element 8A are provided inside. The provided functional ink is dried by the provided drying means 6A. Next, recording ink is applied onto the fabric from the recording ink discharge head mounted on the carriage 5B to form an image, and then the fabric is dried by the drying means 6B.

  FIG. 2 is a partial schematic view of the carriage 5A of the ink jet printing apparatus shown in FIG. 1 as viewed from above.

  In FIG. 2, in the drawing, functional ink is applied to the fabric conveyed from the upper side by the functional ink discharge head. In the figure, PT represents a functional ink ejection head, X1 represents the main scanning direction of the carriage, and X2 represents the transport direction of the fabric.

  FIG. 3 is a partial schematic view of the recording ink ejection carriage 5B of the inkjet textile printing apparatus shown in FIG. 1 as viewed from above.

  In FIG. 3, recording ink is applied to the fabric conveyed from the upper side of the drawing by a recording ink discharge head. C, M, Y, and K indicate recording ink ejection heads corresponding to cyan, magenta, yellow, and black inks, respectively. X1 similarly represents the main scanning direction of the carriage, and X2 represents the conveyance direction of the fabric.

  FIG. 4 is a partial schematic diagram illustrating another example of the configuration of the inkjet textile printing apparatus.

  The inkjet printing apparatus shown in FIG. 4 is an example in which an inkjet head for applying functional ink and an inkjet head for applying recording ink are mounted on the same carriage 5 with respect to the inkjet printing apparatus shown in FIG. The carriage 5 has both an ink jet head for applying functional ink and a recording ink ejection head for applying recording ink. In this example, since only one set of the carriage 5 and its driving means is prepared, the structure of the ink jet textile printing apparatus can be made simple and compact.

  FIG. 5 is a partial schematic view of the carriage 5 of the inkjet printing apparatus shown in FIG. 4 as viewed from above. Recording ink discharge heads C to Y and a functional ink discharge head PT are arranged on the carriage.

  In FIG. 5, after the functional ink is applied to the fabric conveyed from the upper side of the drawing by the functional ink discharge head arranged upstream from the recording ink discharge head, it is provided as a drying means on both sides of the carriage. The obtained far infrared heater IR is dried. Next, after the recording ink is applied to the fabric by the recording ink discharge head, it is dried by the far-infrared heater IR like the functional ink. In the figure, X1 similarly represents the main scanning direction of the carriage, and X2 represents the conveyance direction of the fabric.

  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.

<Preparation of recording ink>
[Preparation of reactive dye ink]
(Preparation of reactive dye ink RY)
The following constituent materials were stirred, mixed, dissolved, filtered through a 0.8 μm filter, and then degassed to prepare a reactive dye ink RY.

Y dye: C.I. I. Reactive Yellow 95 13 parts Ethylene glycol 10 parts Propylene glycol 25 parts Glycerin 3 parts Olphine E1010 (acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)
0.1 part ion exchange water 48.9 parts (Preparation of reactive dye ink RM, reactive dye ink RC, reactive dye ink RBk)
In the preparation of the reactive dye ink RY, C.I. I. A reactive dye ink RM, a reactive dye ink RC, and a reactive dye ink RBk were prepared in the same manner except that the reactive yellow 95 was changed to the following reactive dyes.

<Reactive dye ink RM>
M dye: C.I. I. Reactive Red 24
<Reactive dye ink RC>
C dye: C.I. I. Reactive Blue 72
<Reactive dye ink RBk>
Bk dye: C.I. I. Reactive Black 8
[Preparation of acid dye ink]
(Preparation of acid dye ink AY)
The following constituent materials were stirred, mixed, dissolved, filtered through a 0.8 μm filter, and then deaerated to prepare acid dye ink AY.

Y dye: C.I. I. Acid Yellow 79 5 parts Diethylene glycol 15 parts Glycerin 15 parts Olphine E1010 (acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)
0.3 parts Ion-exchanged water 64.7 parts (Preparation of acid dye ink AM, acid dye ink AC, acid dye ink ABk)
In the preparation of the acid dye ink AY, C.I. I. Acid dye ink AM, acid dye ink AC, and acid dye ink ABk were prepared in the same manner except that Acid Yellow 79 was changed to the following acid dyes.

<Acid dye ink AM>
M dye: C.I. I. Acid Red 249
<Acid dye ink AC>
C dye: C.I. I. Direct Blue 87
<Acid dye ink RBk>
Bk dye: C.I. I. Acid Black 52: 1
[Preparation of disperse dye ink]
(Preparation of dye dispersion)
<Preparation of dye dispersion Y1>
The following constituent materials were dispersed using a sand grinder filled with 85% by volume of 0.3 mm zirconia beads to prepare a dye dispersion Y1. Dispersion stopped when the average particle size reached 200 nm.

Y disperse dye: C.I. I. Disperse Yellow 127 25 parts Glycerin 25 parts Ion-exchanged water 25 parts Dispersant A (sodium lignin sulfonate, Vanillex RN, manufactured by Nippon Paper Chemicals) 12 parts Dispersant B (Floren G-700, manufactured by Kyoeisha Chemical Co., Ltd.) 3 parts < Preparation of Dye Dispersion M1, Dye Dispersion C1, and Dye Dispersion K1>
In the preparation of the dye dispersion Y1, C.I. I. Dye dispersion M1, dye dispersion C1, and dye dispersion K1 were prepared in the same manner except that Disperse Yellow 127 was changed to the following disperse dyes.

<Dye dispersion M1>
M disperse dye: C.I. I. Disperse Red 32
<Dye dispersion C1>
C disperse dye: C.I. I. Disperse Blue 27
<Dye dispersion K1>
K disperse dye: C.I. I. Disperse Black 7
(Preparation of disperse dye ink DY)
The following constituent materials were stirred, mixed, dissolved, filtered through a 0.8 μm filter, and then degassed to prepare a disperse dye ink DY.

Dye dispersion Y1 40 parts Ethylene glycol 40 parts Diethylhexyl sulfosuccinate sodium 0.1 part Antifungal agent: Proxel GXL S (manufactured by Avicia) 0.1 part Ion-exchanged water 19.8 parts (Disperse dye ink DM, disperse dye Preparation of ink DC and disperse dye ink DBk)
In the preparation of the disperse dye ink DY, the disperse dye ink DM and the disperse dye ink DC were the same except that the dye dispersion liquid M1, the dye dispersion liquid C1, and the dye dispersion liquid K1 were used instead of the dye dispersion liquid Y1, respectively. A disperse dye ink DBk was prepared.

[Preparation of pigment ink]
(Preparation of pigment dispersion)
<Preparation of pigment dispersion Y2>
The following constituent materials were dispersed using a sand grinder filled with 85% by volume of 0.3 mm zirconia beads to prepare a pigment dispersion Y2. Dispersion was stopped when the average particle size reached 120 nm.

Y pigment: C.I. I. Pigment Yellow 74 15 parts Styrene-acrylic acid copolymer (John Cryl 678, molecular weight: 8500, acid value: 215 mg KOH / g) 3 parts Dimethylaminoethanol 1.3 parts Ion-exchanged water 80.7 parts <Pigment dispersion M2, Preparation of pigment dispersion C2 and pigment dispersion K2>
In the preparation of the pigment dispersion Y2, the pigment C.I. I. Pigment dispersion M2, pigment dispersion C2, and pigment dispersion K2 were prepared in the same manner except that Pigment Yellow 74 was changed to the following pigments.

<Pigment dispersion M2>
M pigment: C.I. I. Pigment Red 122
<Pigment dispersion C2>
C pigment: C.I. I. Pigment Blue 15: 3
<Pigment dispersion K2>
K pigment: C.I. I. Pigment Black 7
(Preparation of pigment ink PY)
The following constituent materials were stirred, mixed, dissolved, filtered through a 0.8 μm filter, and then degassed to prepare pigment ink PY.

27 parts of pigment dispersion Y2 Water-soluble copolymer aqueous solution (water-soluble copolymer content: 20% by mass, see below)
17 parts triethylene glycol monobutyl ether 8 parts 1,2-hexanediol 6 parts diethylene glycol 12 parts KF-351A (silicon surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.6 parts ion-exchanged water 29.4 parts <water-soluble Preparation of aqueous copolymer solution>
50 g of methyl ethyl ketone was added to a flask equipped with a dropping funnel, a nitrogen introducing officer, a reflux condenser, a thermometer and a stirring device, and heated to 75 ° C. while bubbling with nitrogen gas. Thereto, a mixture comprising 80 g of n-butyl methacrylate, 20 g of acrylic acid, 50 g of methyl ethyl ketone, and 500 mg of a polymerization initiator (AIBN: azobisisobutyronitrile) was dropped from a dropping funnel over 3 hours. After the dropwise addition, the mixture was further heated to reflux for 6 hours. After allowing to cool, the mixture was heated under reduced pressure, and methyl ethyl ketone was distilled off to obtain a polymer residue.

  Next, dimethylaminoethanol equivalent to 1.05 mol of acrylic acid added as a monomer was dissolved in 450 ml of ion-exchanged water, and the polymer residue was added and dissolved therein. Subsequently, the concentration was adjusted with ion-exchanged water to obtain an aqueous solution of a water-soluble copolymer (acid value 117 mgKOH / g) having a water-soluble copolymer content of 20% by mass.

(Preparation of pigment ink PM, pigment ink PC, pigment ink PBk)
In the preparation of the pigment ink PY, the pigment ink PM, the pigment ink PC, and the pigment ink were similarly used except that the pigment dispersion M2, the pigment dispersion C2, and the pigment dispersion K2 were used instead of the pigment dispersion Y2. PBk was prepared.

[Recording ink storage]
Each of the inks prepared above passes the ink through a gas-permeable hollow fiber membrane (manufactured by Mitsubishi Rayon) and decompresses the outer surface side of the hollow fiber membrane with a water flow aspirator, so that the dissolved gas in the ink is reduced. Removed. After degassing, these inks were filled into vacuum packs to prevent air from entering.

<< Preparation of functional ink >>
[Preparation of functional inks PT-1 to PT-16 for reactive dye ink]
Functional inks PT-1 to PT-16 for reactive dye inks having the constitution described in Table 1 were prepared by the following procedure.

  In a predetermined amount of ion exchange water, potassium carbonate, 2-imidazolidinone, each rust inhibitor, propylene glycol, triethylene glycol monobutyl ether and polyethylene glycol 6000 are dissolved in this order, and then filtered through a 0.8 μm filter. Functional inks PT-1 to PT-16 were prepared.

[Preparation of Functional Inks PT-17 to PT-32 for Acid Dye Inks]
Functional inks PT-17 to PT-32 for acid dye inks having the constitution described in Table 2 were prepared by the following procedure.

  After dissolving sodium tripolyphosphate, 2-imidazolidinone, each rust inhibitor, propylene glycol, triethylene glycol monobutyl ether, polyethylene glycol 6000 and register liquid in this order in a predetermined amount of ion-exchanged water, a 0.8 μm filter And functional inks PT-17 to PT-32 were prepared.

[Preparation of functional inks PT-33 to PT-48 for disperse dye ink]
Functional inks PT-33 to PT-48 for disperse dye inks having the composition described in Table 3 were prepared by the following procedure.

  After dissolving citric acid, 2-imidazolidinone, each rust inhibitor, ethylenediaminetetraacetic acid (EDTA) -2Na, propylene glycol, triethylene glycol monobutyl ether and polyethylene glycol 6000 in this order in a predetermined amount of ion-exchanged water And filtered through a 0.8 μm filter to prepare functional inks PT-33 to PT-48.

[Preparation of functional inks PT-49 to PT-64 for pigment ink]
Functional inks PT-49 to PT-64 for pigment inks having the constitution described in Table 4 were prepared by the following procedure.

  Citric acid, each rust inhibitor, ethylenediaminetetraacetic acid (EDTA) -2Na, ethylene glycol and glycerin are dissolved in this order in a predetermined amount of ion-exchanged water, and then filtered through a 0.8 μm filter, and the functional ink PT- 49-PT-64 were prepared.

  In Tables 1 to 4, the details of each additive described in abbreviations are as follows.

<General additives>
STP: sodium tripolyphosphate (active ingredient 57 mass%, manufactured by Kanto Chemical Co., Inc.)
PG: Propylene glycol TEGBE: Triethylene glycol monobutyl ether (Butizenol 30, manufactured by Kyowa Hakko Chemical Co., Ltd.)
EG: Ethylene glycol Gly: Glycerin PEG: Polyethylene glycol 6000
RL: Resistor liquid (sodium metanitrobenzenesulfonate solution, manufactured by Senka)
EDTA-2Na: Ethylenediaminetetraacetic acid, 2Na
<anti-rust>
W-410: Killeslite W-410 (rust preventive mainly composed of fatty acid salt, 35% by mass of active ingredient, manufactured by Kirest Co., Ltd.)
W-511: Killeslite W-511 (rust preventive agent based on organic acid amine salt, active ingredient 45 mass%, manufactured by Kirest Co., Ltd.)
PL: potassium laurate SS: sodium sebacate OA / TEA: oleic acid / triethanolamine salt SB: sodium benzoate (Sodium Benzoate)
Rust inhibitor 1: p-tert-butylbenzoic acid / triethanolamine salt SN: sodium nitrite (Sodium Nitrite)
TEA: Triethanolamine A308: Amit 308 (polyoxyethylene stearylamine, manufactured by Kao Corporation)
Q24P: Cotamine 24P (lauryltrimethylammonium chloride, active ingredient 27 mass%, manufactured by Kao Corporation)
A24B: Amphital 24B (Lauryldimethylaminoacetic acid betaine, 27 mass% active ingredient, manufactured by Kao Corporation)
BTZ: Benzotriazole Example 1
[Preparation of functional ink]
1 L of each of the functional inks PT1 to PT16 prepared above was dispensed into a plastic bottle, each was filled with a SUS430 piece having a thickness of 1 mm and a size of 10 cm × 10 cm, and stored in a thermostatic bath at 60 ° C. for 2 weeks. . Moreover, what used 42 alloy (nickel-iron alloy containing 42% of nickel) instead of SUS430 was similarly prepared, and it similarly stored for 2 weeks in a 60 degreeC thermostat. Then, each was taken out from the thermostat, each functional ink was cooled to room temperature, filtered through a 0.8 μm filter, and then deaerated. In the deaeration process, ink was passed through a gas permeable hollow fiber membrane (manufactured by Mitsubishi Rayon), and the dissolved gas in the ink was removed by reducing the pressure on the outer surface of the hollow fiber membrane with a water aspirator. . After degassing, these functional inks were filled into a vacuum pack to prevent air from entering.

[Preparation of Print Samples 1-16]
A print sample was prepared using an ink jet textile printing apparatus having the configuration shown in FIGS.

  First, each of the functional inks prepared according to the above method is loaded into the functional ink discharge head of the carriage 5A shown in FIG. 1, and the prepared reactive dye is used as the recording ink in the recording ink discharge head of the carriage 5B. Inks RY, RM, RC, RBk were loaded.

Next, while transporting the cotton 200 as the fabric P in the direction of the arrow in FIG. 1, the functional ink is applied to the entire surface of the fabric so that the amount of each functional ink is 12 ml / m ² from the functional ink discharge head of the carriage 5A. After the application, the hot air was applied by 6A.

Subsequently, each recording ink was applied to the fabric from the recording ink ejection head of the carriage 5B, and a pattern was printed so that the area of the white background portion was 50% of the entire fabric, and then dried by the hot air applying means 6B. . The amount of recording ink applied was adjusted so that the amount of recording ink applied was 9 ml / m ² in a single color solid image. In addition, the interval between the carriage 5A and the carriage 5B and the conveyance speed of the fabric P were adjusted so that the interval from when the functional ink was applied to the fabric until the recording ink was applied to the same position was 60 seconds. .

  Next, the printed fabric P was subjected to a steaming treatment at a temperature of 100 ° C. for 15 minutes, then washed with water, subjected to a soaping treatment at 60 ° C., further washed with water, and then dried to obtain printed samples 1 to 1. 16 was obtained.

[Evaluation of print samples]
In the preparation of each sample, immediately after the steaming process and immediately after the water washing after the soaping process, the colored state of the white fabric portion was visually observed and evaluated based on the following evaluation criteria. The obtained results are shown in Table 5.

◎: No coloring is observed in the white background portion ○: Slight coloring is observed in the white background portion △: Slight coloring is observed in the white background portion, but is a practically acceptable level ×: Clear coloring in the white background portion Is recognized and is a practically problematic quality

  As is apparent from the results shown in Table 5, the printed matter produced using the functional ink of the present invention and the reactive dye ink produced coloring of the white background of the fabric due to corrosion of the metal member, as compared with the comparative example. It can be seen that is suppressed.

Example 2
[Preparation of Print Samples 17 and 18]
Print samples 17 and 18 were produced using an ink jet textile printing apparatus having the functional ink ejection head and the recording ink ejection head shown in FIGS. Although not shown, SUS430 piping was used in the functional ink flow path system of the ink jet textile printing apparatus, except for the portion that required flexibility.

  First, functional ink is introduced into the functional ink ejection head PT of the carriage 5 and the above-described reactive dye inks RY, RM, RC, RBk are used as recording inks in the recording ink ejection heads C, M, Y, and K. Was introduced. As the functional ink, the prepared functional inks PT-1 and PT-16 were used.

Next, using cotton 200 as the fabric P, a pattern in which functional ink is formed from the recording ink described later from the functional ink discharge head PT of the carriage 5 while the fabric P is conveyed in the direction of the arrow shown in FIG. After giving it imagewise so that it would be 2 to 3 mm wider than the outline of the film, it was dried using a far infrared heater IR. The amount of functional ink applied was adjusted to be 12 ml / m ² when uniformly applied to the entire surface of the fabric.

Subsequently, after recording ink was applied to the fabric from the recording ink discharge heads C, M, Y, and K and the pattern was printed so that the area of the white background portion was 50% of the entire fabric, the far infrared heater IR was used. Dried. The amount of recording ink applied was adjusted to 9 ml / m ² in a single color solid image. Further, the interval a between the functional ink ejection head and the recording ink ejection head is set so that the interval between the application of the functional ink to the fabric and the application of the recording ink at the same position is 10 seconds. It was adjusted.

Under such conditions, printing was continuously performed for one month at an operation time of 8 hours per day. The print amount per hour was about 20 m ² .

  Next, the printed fabric of the first month was steamed at a temperature of 100 ° C. for 15 minutes, washed with water, soaped at 60 ° C., further washed with water and dried to obtain a printed sample. .

[Evaluation of print samples]
In the same manner as in the method described in Example 1, the coloration of the white fabric background was evaluated, and the results obtained are shown in Table 6.

  As is clear from the results shown in Table 6, the printed matter produced using the functional ink of the present invention and the reactive dye ink was made of metal in the functional ink flow path system of the ink jet printing apparatus, as compared with the comparative example. It can be seen that the occurrence of coloring of the white background of the fabric is suppressed even with this pipe.

Example 3
[Preparation of functional ink]
1 L of each of the prepared functional inks PT17 to PT32 was taken into a plastic bottle, each was filled with a SUS430 piece of 10 mm × 10 cm size with a thickness of 1 mm, and stored in a thermostatic bath at 60 ° C. for 2 weeks. . Moreover, what used 42 alloy (nickel-iron alloy containing 42% of nickel) instead of SUS430 was similarly prepared, and it similarly stored for 2 weeks in a 60 degreeC thermostat. Then, each was taken out from the thermostat, each functional ink was cooled to room temperature, filtered through a 0.8 μm filter, and then deaerated. In the deaeration process, ink was passed through a gas permeable hollow fiber membrane (manufactured by Mitsubishi Rayon), and the dissolved gas in the ink was removed by reducing the pressure on the outer surface of the hollow fiber membrane with a water aspirator. . After degassing, these functional inks were filled into a vacuum pack to prevent air from entering.

[Preparation of Print Samples 19 to 34]
Using the prepared acid dye inks AY, AM, AC, and ABk as the recording ink, each functional ink and recording ink were applied to a fabric and dried in the same manner as in the method described in Example 1.

  Next, the printed fabric was steamed at a temperature of 100 ° C. for 30 minutes, washed with water, soaped at 40 ° C., further washed with water and dried to obtain print samples 19 to 34.

[Evaluation of print samples]
Each of the produced print samples was evaluated in the same manner as described in Example 1 for the coloring of the white background portion of the print sample, and the results obtained are shown in Table 7.

  As is apparent from the results shown in Table 7, the printed matter produced using the functional ink of the present invention and the acid dye ink produced coloring of the white background of the fabric due to the corrosion of the metal member as compared with the comparative example. It turns out that it is suppressed.

Example 4
[Preparation of Print Samples 35 and 36]
Using the acid dye inks AY, AM, AC and ABk as the recording ink and the functional inks PT-17 and PT-32 as the functional ink, the same method as described in Example 2 is used for one month. Printing was performed continuously.

  Next, the printed fabric of the first month is subjected to a steaming process at a temperature of 100 ° C. for 30 minutes, washed with water, soaped at 40 ° C., further washed with water and dried, and printed samples 35 and 36 Got.

[Evaluation of Print Samples 35 and 36]
The printed samples 35 and 36 produced above were evaluated in the same manner as described in Example 2, and the results obtained are shown in Table 8.

  As is clear from the results shown in Table 8, the printed matter produced using the functional ink of the present invention and the acid dye ink was made of metal in the functional ink flow path system of the ink jet printing apparatus, compared to the comparative example. It turns out that generation | occurrence | production of coloring of the fabric white background part is suppressed even if it uses piping.

Example 5
[Preparation of functional ink]
1 L of each of the functional inks PT33 to PT48 prepared above was dispensed into a plastic bottle, each was filled with a SUS430 piece of 10 mm × 10 cm size with a thickness of 1 mm, and stored in a thermostatic bath at 60 ° C. for 2 weeks. . Moreover, what used 42 alloy (nickel-iron alloy containing 42% of nickel) instead of SUS430 was similarly prepared, and it similarly stored for 2 weeks in a 60 degreeC thermostat. Then, each was taken out from the thermostat, each functional ink was cooled to room temperature, filtered through a 0.8 μm filter, and then deaerated. In the deaeration process, ink was passed through a gas permeable hollow fiber membrane (manufactured by Mitsubishi Rayon), and the dissolved gas in the ink was removed by reducing the pressure on the outer surface of the hollow fiber membrane with a water aspirator. . After degassing, these functional inks were filled into a vacuum pack to prevent air from entering.

[Preparation of Print Samples 37 to 52]
Using the prepared disperse dye inks DY, DM, DC, and DBk as recording inks, each functional ink and recording ink were applied to a fabric and dried in the same manner as described in Example 1.

  Next, the printed fabric was steamed at a temperature of 130 ° C. for 30 minutes, washed with water, soaped at 80 ° C., further washed with water and dried to obtain print samples 37 to 52.

[Evaluation of print samples]
Each of the produced print samples was evaluated in the same manner as described in Example 1 for coloring the white background portion of the print sample, and the results obtained are shown in Table 9.

  As is clear from the results shown in Table 9, the printed matter produced using the functional ink of the present invention and the disperse dye ink produced coloring of the white background portion of the fabric due to the corrosion of the metal member as compared with the comparative example. It turns out that it is suppressed.

Example 6
[Preparation of Print Samples 53 and 54]
Using the disperse dye inks DY, DM, DC, and DBk as the recording ink and the functional inks PT-33 and PT-48 as the functional ink, the same method as that described in Example 2, for one month. Printing was performed continuously.

  Next, the printed fabric of the first month is subjected to a steaming process at a temperature of 130 ° C. for 30 minutes, washed with water, soaped at 80 ° C., further washed with water and dried, and printed samples 53 and 54 Got.

[Evaluation of Print Samples 53 and 54]
In the same manner as in the method described in Example 2, the produced print samples 53 and 54 were evaluated, and the obtained results are shown in Table 10.

  As is clear from the results shown in Table 10, the printed matter produced using the functional ink of the present invention and the disperse dye ink was made of metal in the functional ink flow path system of the ink jet printing apparatus as compared with the comparative example. It turns out that generation | occurrence | production of coloring of the fabric white background part is suppressed even if it uses piping.

Example 7
[Preparation of functional ink]
1 L of each of the prepared functional inks PT49 to PT64 was dispensed into a plastic bottle, and each piece was sealed with a SUS430 piece of 10 mm × 10 cm size having a thickness of 1 mm, and stored in a constant temperature bath at 60 ° C. for 2 weeks. . Moreover, what used 42 alloy (nickel-iron alloy containing 42% of nickel) instead of SUS430 was similarly prepared, and it similarly stored for 2 weeks in a 60 degreeC thermostat. Then, each was taken out from the thermostat, each functional ink was cooled to room temperature, filtered through a 0.8 μm filter, and then deaerated. In the deaeration process, ink was passed through a gas permeable hollow fiber membrane (manufactured by Mitsubishi Rayon), and the dissolved gas in the ink was removed by reducing the pressure on the outer surface of the hollow fiber membrane with a water aspirator. . After degassing, these functional inks were filled into a vacuum pack to prevent air from entering.

[Preparation of Print Samples 55 to 70]
Using the prepared pigment inks PY, PM, PC, and PBk as the recording ink, each functional ink and recording ink was applied to a fabric and dried in the same manner as described in Example 1.

  Next, the printed fabric was heated and dried at a temperature of 140 ° C. for 1 minute to obtain printed samples 55 to 70.

[Evaluation of print samples]
The produced print samples 55 to 70 are evaluated in the same manner as described in Example 1 for coloring the white background portion of the print sample, and the obtained results are shown in Table 11.

  As is apparent from the results shown in Table 11, the printed matter produced using the functional ink and the pigment ink of the present invention is less affected by the coloration of the white fabric portion due to the corrosion of the metal member than the comparative example. You can see that.

Example 8
[Preparation of Print Samples 71 and 72]
The above-described pigment inks PY, PM, PC, and PBk are used as recording inks, and the above-described functional inks PT-49 and PT-64 are used as functional inks, in the same manner as in the method described in Example 2, for one month. Printing was performed continuously.

  Next, the printed fabric of the first month was heat-dried at a temperature of 140 ° C. for 1 minute to obtain printed samples 71 and 72.

[Evaluation of Print Samples 71 and 72]
In the same manner as in the method described in Example 2, the produced print samples 71 and 72 were evaluated, and the obtained results are shown in Table 12.

  As is clear from the results shown in Table 12, the printed matter produced using the functional ink and the pigment ink of the present invention is different from the comparative example in that a metal pipe is provided in the functional ink flow path system of the ink jet printing apparatus. It can be seen that the occurrence of coloring of the white fabric background is suppressed even when using.

DESCRIPTION OF SYMBOLS 1 Adhesive belt 2 Support roll 3 Conveyance roll 4 Nip roll 5, 5A, 5B Carriage 7, 7A, 7B Fan 8, 8A, 8B Heating element 6, 6A, 6B Hot air provision means PT Pretreatment agent discharge head C, M , Y, K Recording ink ejection head

Claims (9)

  An inkjet ink set for textile printing comprising at least a functional ink containing a rust inhibitor and a recording ink containing a colorant.   The inkjet ink set for textile printing according to claim 1, wherein the functional ink contains an alkali agent or an acid compound.   The inkjet for printing according to claim 1 or 2, wherein the rust inhibitor is at least one compound selected from organic acids, salts of organic acids, amines, nitrites, and benzotriazoles. Ink set.   The inkjet ink set for textile printing according to any one of claims 1 to 3, wherein the functional ink contains a rust preventive agent in an amount of 0.1 mass% to 5.0 mass%.   The inkjet ink set for textile printing according to any one of claims 1 to 4, wherein the functional ink contains 2-imidazolidinone.   An inkjet printing method using the inkjet ink set for printing according to any one of claims 1 to 5, wherein a functional ink is applied to a fabric using an inkjet head, and then a recording ink is applied to the fabric. An inkjet printing method characterized by the above.   The inkjet printing method according to claim 6, wherein the recording ink is applied to the fabric after the functional ink applied to the fabric is dried by heating.   The inkjet printing method according to claim 7, wherein a heating unit for heating and drying the functional ink is mounted on an inkjet printer.   9. The inkjet printing method according to claim 8, wherein the heating means for heating and drying the functional ink is mounted on a carriage on which an inkjet head is mounted.

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