JP2018003184A - Inkjet printing method and ink set for use therein - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet printing method that makes it possible to form a printed article excellent in the color development of an image and friction fastness.SOLUTION: An inkjet printing method is performed by attaching, to a fabric treated with a pretreatment liquid containing a cationic organic compound, a printing ink composition containing a urethane resin having a crosslinkable group, and heating the fabric.SELECTED DRAWING: None

Description

  The present invention relates to an inkjet textile printing method and an ink set used therefor.

  The ink jet recording method is a method of recording by ejecting small ink droplets from fine nozzles and attaching them to a recording medium. This method has a feature that a high-resolution and high-quality image can be recorded at a high speed with a relatively inexpensive apparatus. In the ink jet recording method, there are a large number of consideration factors including the nature of the ink used, the stability in recording, and the quality of the obtained image, and research on not only the ink jet recording apparatus but also the ink composition to be used is active. is there.

  Moreover, dyeing | staining (printing) of fabric etc. is also performed using the inkjet recording method. Conventionally, screen printing methods, roller printing methods, and the like have been used as printing methods for fabrics (woven fabrics and non-woven fabrics). From the viewpoints of various small-scale productivity and immediate printability, etc., an inkjet recording method should be applied. Has been studied in various ways.

  Studies have also been made on so-called pigment printing, in which a fabric is printed by blending an ink composition with a pigment and a fixing resin. In the case of pigment printing, it is important to physically fix the pigment to the fabric fibers and the like.

  In Patent Documents 1 to 3, in pigment printing, before an ink composition is attached to a cloth, a treatment liquid containing a polyvalent metal salt called a reaction liquid, a pretreatment liquid, or the like is attached to the cloth, thereby Attempts to improve color development have been disclosed. Further, such a document describes that the ink composition contains a crosslinkable resin for the purpose of enhancing the fastness of the image.

JP 2013-194122 A JP 2014-148564 A Japanese Patent Laying-Open No. 2015-083629

  In pigment printing, the use of a pretreatment liquid containing a polyvalent metal salt reacts with the ink composition to fix the colorant at an early stage, thereby preventing the ink composition from penetrating into the fabric and improving the color developability. Can be expected. However, in such a technique, since the color developability is improved by keeping the pigment near the surface of the fabric, on the other hand, the fastness (rub resistance) of the image tends to be insufficient. In the above prior art documents, an attempt is made to increase the fastness of an image by incorporating a crosslinkable resin into the ink composition, but the fastness of the obtained image is still insufficient.

  One of the objects according to some embodiments of the present invention is to provide an ink-jet printing method and an ink set suitable for the same, which can form a printed material excellent in image coloring and friction fastness. .

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

One aspect of the inkjet textile printing method according to the present invention is as follows:
For a fabric treated with a pretreatment liquid containing a cationic organic compound,
A printing ink composition containing a urethane-based resin having a crosslinkable group is attached;
This is done by heating the fabric.

  According to such an ink-jet printing method, the cationic organic compound can retain the color material contained in the printing ink composition in the vicinity of the surface of the fabric, thereby obtaining an image (printed product) having sufficient color developability. In addition, the urethane-based resin having a crosslinkable group is crosslinked by being heated, and the entanglement between the fabric and the cationic organic compound, and the entanglement between the cationic organic compound and the crosslinked urethane-based resin, etc. Thus, the coloring material can be sufficiently fixed to the fabric, and an image (printed product) having good fastness can be obtained.

In the inkjet printing method according to the present invention,
The textile printing ink composition may further contain a pigment.

In the inkjet printing method according to the present invention,
The cationic organic compound may be at least one of a cationic polymer and a cationic surfactant.

  According to such an ink jet printing method, the interaction between the cationic organic compound and the fabric, and the interaction between the cationic organic compound and the crosslinked product of the urethane resin having a crosslinkable group are further strengthened. In addition, an image (printed product) having better fastness can be obtained.

In the inkjet printing method according to the present invention,
The urethane resin may have a polycarbonate skeleton or a polyether skeleton.

  According to such an ink-jet printing method, it is possible to obtain a printed material having further excellent friction fastness.

In the inkjet printing method according to the present invention,
The urethane resin may have an elongation at break of 170% or more.

  According to such an ink jet textile printing method, it is possible to obtain a textile print having a better texture.

One aspect of the ink set for inkjet textile printing according to the present invention is as follows:
A pretreatment liquid containing a cationic organic compound;
A printing ink composition containing a urethane-based resin having a crosslinkable group; and
including.

According to such an ink set, the cationic organic compound contained in the pretreatment liquid keeps the color material contained in the printing ink composition near the surface of the fabric (printing object) and has an adequate color developability. (Printed material) can be obtained, and when the urethane resin having a crosslinkable group is crosslinked, the fabric and the cationic organic compound are entangled, and the cationic organic compound and the crosslinked urethane resin are entangled, Therefore, the coloring material can be sufficiently fixed to the fabric, and an image (printed product) having good fastness can be obtained.

  Several embodiments of the present invention will be described below. Embodiment described below demonstrates an example of this invention. The present invention is not limited to the following embodiments, and includes various modified embodiments that are implemented within a range that does not change the gist of the present invention. Note that not all of the configurations described below are essential configurations of the present invention.

1. Inkjet printing method The inkjet printing method of the present embodiment includes a step of treating a fabric with a pretreatment liquid containing a cationic organic compound, and a printing containing a urethane-based resin having a crosslinkable group with respect to the treated fabric. At least a step of attaching the ink composition and a step of heating the fabric. Hereinafter, the textile printing method according to the present embodiment will be described in the order of the fabric and the textile printing method.

1.1. Fabric The inkjet printing method according to the present embodiment is performed using a fabric. The material constituting the fabric is not particularly limited. For example, natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; and biodegradable materials such as polylactic acid. Examples thereof include fibers, and these blended fibers may be used. As the fabric, the above-described fibers may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric. Among these, the fabric used in the present embodiment is more preferably formed of fibers containing cellulose such as cotton and hemp. By using such a fabric, better fixability of the pigment can be obtained.

  The fabric weight used in this embodiment is 1.0 oz (ounces) to 10.0 oz, preferably 2.0 oz to 9.0 oz, more preferably 3.0 oz to 8.0 oz, and even more preferably. Is in the range of 4.0 oz to 7.0 oz. In the textile printing method of the present embodiment, since the pretreatment liquid described later is used, the cationic organic compound can be appropriately arranged when the pretreatment liquid is applied to the fabric having such a weight per unit area. Good pigment printing can be realized. In other words, if the fabric weight is within such a range, the pretreatment liquid can be sufficiently applied, and good printing can be performed by the printing method of the present embodiment. Furthermore, since the textile printing method of the present embodiment uses a pretreatment liquid, it can be applied to a plurality of types of fabrics having different basis weights, and good textile printing can be performed.

1.2. Printing Method Next, the printing method according to the present embodiment will be described for each process.

1.2.1. The step of attaching the pretreatment liquid to the fabric The step of attaching the pretreatment liquid (described later) to the fabric is a step of applying the pretreatment liquid to at least a partial region of the fabric. In this step, the pretreatment liquid is preferably applied so that the amount of the pretreatment liquid is 100 mg / inch ² or more and 3000 mg / inch ² or less, and more preferably 130 mg / inch ² or more and 1500 mg / inch ² or less. preferably, it is more preferable to apply such that the 193 mg / inch ² or more 500 mg / inch ² or less. By making the adhesion amount of the pretreatment liquid 0.02 g / cm ² or more, it becomes easy to uniformly apply the pretreatment liquid to the fabric, so that color unevenness of the image can be suppressed. Moreover, blurring of an image can be suppressed by setting the adhesion amount of the pretreatment liquid to 0.5 g / cm ² or less. Further, the amount of the pretreatment liquid attached is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, based on the mass per area of the fabric.

In this step, it is preferable to apply so that the adhesion amount of the cationic organic compound contained in the pretreatment liquid applied to the fabric is 7.5 μmol / cm ² or more and 40 μmol / cm ² or less, and 12 μmol / cm ² or more. It is more preferable to apply so that it may become 30 micromol / cm < ² > or less. By applying the cationic organic compound so that the adhesion amount is 10 μmol / cm ² or more, the color developability of the recorded image is improved. Moreover, the fastness of the image recorded becomes still more favorable by providing so that the adhesion amount of a cationic organic compound may be 40 micromol / cm < ² > or less.

  Examples of the method of applying the pretreatment liquid to the fabric include a method of immersing the fabric in the pretreatment liquid (dip coating), and a method of applying the pretreatment liquid with a spatula, roller, brush, roll coater, or the like (roller coating). ), A method of spraying the pretreatment liquid with a spray device or the like (spray coating), a method of spraying the pretreatment liquid with an ink jet method (inkjet coating), and the like, and any method may be used. Among these, it is preferable to use contact-type or non-contact-type methods such as dip coating, roller coating, spray coating, etc., because the apparatus configuration is simple and the pretreatment liquid can be quickly applied. These methods may be combined. Inkjet coating is more preferable because the pretreatment liquid can be easily and accurately applied to a predetermined position, and the amount of the pretreatment liquid used can be reduced.

  The textile printing method according to the present embodiment may include a pretreatment liquid drying step of drying the pretreatment liquid applied to the fabric after the step of attaching the pretreatment liquid. The pretreatment liquid may be dried by natural drying, but drying with heating is preferable from the viewpoint of improving the drying speed. When heating is performed in the drying step of the pretreatment liquid, the heating method is not particularly limited, and examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, and a thermofix method. Moreover, as a heat source of heating, although not limited to the following, infrared (lamp) is mentioned, for example.

1.2.2. The step of adhering the textile printing ink composition to the fabric by the ink jet method The step of adhering the textile printing ink composition (described later) to the fabric by the ink jet method is at least one of the regions to which the pretreatment liquid is applied in the step of adhering the pretreatment liquid. In this step, the textile printing ink composition is applied to the part by an ink jet method. As a result, the components such as pigments contained in the textile printing ink composition react with or interact with the cationic organic compound, so that the components such as pigments are aggregated, so that an image having excellent color developability can be obtained. Furthermore, the interaction between the cationic organic compound and the crosslinked product of the urethane resin having a crosslinkable group in the printing ink composition can be caused, and the friction fastness of the recorded image is also improved.

  In this step, an image is printed on the fabric by discharging droplets of the printing ink composition from the nozzles of the inkjet recording head and attaching the droplets to the fabric. As a result, a printed product (printed product) is obtained in which an image made of the printing ink composition is printed on the fabric.

  Any method may be used as an ink jet recording method for discharging a textile printing ink composition, and examples thereof include a charge deflection method, a continuous method, and an ondenmand method (piezo method, bubble jet (registered trademark) method). Among these ink jet recording systems, a system using a piezo type ink jet recording apparatus is more preferable from the viewpoints of high definition and downsizing of the apparatus.

In this step, it is preferable to apply to the fabric so that the amount of the printing ink composition attached is 1.5 mg / cm ² or more and 6 mg / cm ² or less, so that the amount is 2 mg / cm ² or more and 5 mg / cm ² or less. More preferably, it is applied to the fabric. When the printing ink composition adhesion amount is 1.5 mg / cm ² , the color development of the recorded image tends to be good, and the printing ink composition adhesion amount is 6 mg / cm ² or less. Thus, the drying property of the recorded image is improved, and for example, bleeding of the image can be suppressed.

1.2.3. Step of Heating Fabric The textile printing method according to this embodiment includes a heating step of heating the ink composition (image) applied to the fabric.

  The heating method for heating the ink composition applied to the fabric is not particularly limited, and examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, a hot air drying method, and a thermofix method. . Moreover, as a heat source of heating, although not limited to the following, infrared (lamp) is mentioned, for example.

  The heating temperature for heating the ink composition applied to the fabric is not limited to this, but is preferably 80 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 180 ° C. or lower. preferable. However, the heating temperature (attainment temperature) is a temperature that is at least the temperature at which the crosslinkable group of the urethane-based resin having a crosslinkable group described below is activated. Although the details will be described later, the crosslinkable group is chemically protected (capping or blocking), and is deprotected and activated by application of heat to bond (eg, urethane bond, urea bond, allophanate bond). Will form. Moreover, since three or more crosslinkable groups of the urethane-based resin having a crosslinkable group are provided in one molecule, a crosslinked structure is formed by the reaction of the crosslinkable group. In this specification, the urethane resin is a urethane bond, urea bond, or allophanate formed by reacting an isocyanate group with another reactive group (for example, a hydroxyl group, an amino group, a urethane bond group, etc.). It refers to a resin containing bonds and the like. Therefore, in this specification, for example, urea resin is included in urethane resin.

  By this step, the crosslinkable group of the urethane resin having a crosslinkable group contained in the textile printing ink composition is activated, and a crosslinked structure of the urethane resin is generated. As a result, a robust film of urethane resin is formed, and for example, the color material is fixed to the fabric. In addition, since the pretreatment liquid adheres to the fabric as described above, a phenomenon such as the cationic organic compound contained in the pretreatment liquid invades the network of the crosslinked urethane resin, The image can be firmly fixed to the fabric.

  When the heating temperature is within the above range, damage to the fabric can be reduced, or film formation of a resin (may include other resins) contained in the textile printing ink composition can be promoted. In addition, the heating temperature in this heating process means the temperature of the image surface formed in the fabric, for example, it measures using a non-contact thermometer (trade name “IT2-80”, manufactured by Keyence Corporation). Can do. Further, the heating time is not limited to this, but for example, it may be 30 seconds or longer and 20 minutes or shorter.

1.3. Action Effect According to the ink jet printing method of the present embodiment, the cationic colorant contained in the printing ink composition is held near the surface of the fabric by the cationic organic compound, and an image (printed product) having sufficient color developability is obtained. In addition, the urethane-based resin having a crosslinkable group is crosslinked by being heated, the entanglement between the fabric and the cationic organic compound, and the entanglement between the cationic organic compound and the urethane-based resin crosslinked, etc. By this interaction, the coloring material can be sufficiently fixed to the fabric, and an image (printed product) having good fastness can be obtained.

2. Pretreatment liquid The pretreatment liquid according to the present embodiment is used in the above-described ink jet textile printing method in which a textile ink composition described later is attached to a fabric by an ink jet method. More specifically, the pretreatment liquid according to the present embodiment is attached to the fabric, and then the printing ink composition is attached to the fabric by an ink jet method to be used for textile printing.

2.1. Cationic Organic Compound The pretreatment liquid of this embodiment contains at least a cationic organic compound. The cationic organic compound aggregates or thickens the components of the printing ink composition (described later). That is, the cationic organic compound has a function of aggregating the pigment by interacting with at least a part of components such as a pigment and a resin contained in the textile printing ink composition. Thereby, it is possible to improve the color developability and fixability of an image recorded by the textile printing ink composition. Further, the cationic organic compound can increase the viscosity (thickening) of the printing ink composition by interacting with at least a part of components such as pigments and resins contained in the printing ink composition. Thereby, it can suppress that a textile-printing ink composition permeate | penetrates the inside of a fabric too much, and can improve color developability. Further, there are cases where bleeding and bleeding can be reduced by increasing the viscosity of the textile printing ink composition.

  Although it does not specifically limit as a cationic organic compound, Organic acid salt, a cationic resin, a cationic surfactant, etc. can be used. Among the cationic organic compounds, it is preferable to use at least one selected from a cationic resin and a cationic surfactant from the viewpoint of excellent reactivity with components contained in the textile printing ink composition.

  By cationic organic compounds, the surface charge of the components contained in the printing ink composition is neutralized or the pH of the printing ink composition is changed to cause the components to aggregate or precipitate, thereby aggregating or thickening the printing ink composition. . Examples of the component that reacts with the cationic organic compound contained in the textile printing ink composition include pigments and resins described below.

  Examples of organic acid salts include polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, and orthophosphoric acid. And salts of pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid and the like. The counter ion (cation) of the organic acid salt is not particularly limited, and examples thereof include ions of sodium, potassium, calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, iron and the like. An organic acid salt may be used individually by 1 type, and may use 2 or more types together.

  Examples of the cationic resin include a cationic urethane resin, a cationic olefin resin, and a cationic allylamine resin.

  As the cationic urethane resin, known ones can be appropriately selected and used. Examples of the cationic urethane-based resin include hydran CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, CP-7610 (trade name, Dainippon Ink and Chemicals, Inc. Manufactured), Superflex 600, 610, 620, 630, 640, 650 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), urethane emulsion WBR-2120C, WBR-2122C (trade name, manufactured by Taisei Fine Chemical Co., Ltd.), etc. Can be used.

The cationic olefin resin has an olefin such as ethylene or propylene in the structural skeleton, and a known one can be appropriately selected and used. The cationic olefin resin may be in an emulsion state dispersed in a solvent containing water, an organic solvent, or the like. As the cationic olefin resin, commercially available products can be used, and examples thereof include Arrow Base CB-1200, CD-1200 (trade name, manufactured by Unitika Ltd.) and the like.

  As the cationic allylamine resin, known resins can be appropriately selected and used. For example, polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride / diallylamine hydrochloride copolymer, allylamine acetate / diallylamine acetic acid Salt copolymer, allylamine acetate / diallylamine acetate copolymer, allylamine hydrochloride / dimethylallylamine hydrochloride copolymer, allylamine / dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amide sulfate, polymethyldiallylamine acetic acid Salt, polydiallyldimethylammonium chloride, diallylamine acetate / sulfur dioxide copolymer, diallylmethylethylammonium ethyl sulfate - sulfur dioxide copolymers, methyl diallyl amine hydrochloride-sulfur dioxide copolymers, diallyldimethylammonium chloride-sulfur dioxide copolymers, diallyldimethylammonium chloride-acrylamide copolymer and the like.

  As such a cationic allylamine resin, commercially available products can be used. For example, PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, PAA-HCL-3L, PAA-HCL- 10L, PAA-H-HCL, PAA-SA, PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15C, PAA-25, PAA-H-10C, PAA-D11- HCL, PAA-D41-HCL, PAA-D19-HCL, PAS-21CL, PAS-M-1L, PAS-M-1, PAS-22SA, PAS-M-1A, PAS-H-1L, PAS-H- 5L, PAS-H-10L, PAS-92, PAS-92A, PAS-J-81L, PAS-J-81 (trade name, Nittobo Medical Association Etsu Chemical Co., Ltd.), Haimo Neo-600, Haimorokku Q-101, Q-311, Q-501, high-Max SC-505, SC-505 (trade name, can be used Haimo Co., Ltd.), and the like.

  Examples of the cationic surfactant include primary, secondary and tertiary amine salt type compounds, alkylamine salts, dialkylamine salts, aliphatic amine salts, fatty acid amidoamines, benzalkonium salts, quaternary salts. Ammonium salts, quaternary alkyl ammonium salts, alkyl pyridinium salts, sulfonium salts, phosphonium salts, onium salts, imidazolinium salts, alkyl betaines, fatty acid amide betaines, alkyl amine oxides and the like can be mentioned. Specifically, alkyltrimethylammonium salts, dialkyldimethylammonium salts and alkyldimethylbenzylammonium salts are exemplified as quaternary ammonium series, and N-methylbishydroxyethylamine fatty acid ester hydrochloride is exemplified as amine salt series. Further, for example, lauryl Amine, palmamine, rosinamine and other hydrochlorides, acetates, lauryltrimethylammonium chloride, cetyltributylammonium chloride, benzyltributylammonium chloride, benzalkonium chloride, dimethylethyllaurylammonium ethylsulfate, dimethylethyloctylammonium ethylsulfate, Trimethyllauryl ammonium hydrochloride, cetylpyridinium chloride, cetylpyridinium bromide, dihydroxyethyl Uriruamin, decyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl ammonium chloride, hexadecyl dimethyl ammonium chloride, octadecyl dimethyl ammonium chloride, and the like.

As such a cationic surfactant, commercially available products can be used. For example, cationogen TML, cationogen TMP, cationogen TMS, cationogen ES-O, cationogen ES-L, cationogen ES-L-9, cationogen ES -P (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Amorgen S-H, Amorgen K, Amorgen CB-H, Amorgen HB-C, Amorgen AOL (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.
The total content (solid content) of the cationic organic compound with respect to the entire pretreatment liquid of the present embodiment can be appropriately determined so that the above-described effects are exhibited. On the other hand, it is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 25% by mass or less, further preferably 1% by mass or more and 20% by mass or less, and particularly preferably 1% by mass. % To 15% by mass.

2.2. Other components 2.2.1. Water The pretreatment liquid according to this embodiment may contain water. Examples of water include water from which ionic impurities have been removed as much as possible, such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of bacteria and fungi can be prevented when the pretreatment liquid is stored for a long period of time.

  The water content is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more with respect to the total amount of the pretreatment liquid. The water in the pretreatment liquid includes, for example, a resin particle dispersion used as a raw material and water to be added. When the water content is 30% by mass or more, the pretreatment liquid can have a relatively low viscosity. Moreover, the upper limit of the water content is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less with respect to the total amount of the pretreatment liquid.

2.2.2. Water-soluble organic solvent The pretreatment liquid of this embodiment may contain a water-soluble organic solvent. In some cases, the water-soluble organic solvent can improve the wettability of the pretreatment liquid with respect to the recording medium. Examples of the water-soluble organic solvent include at least one of esters, alkylene glycol ethers, cyclic esters, and alkoxyalkylamides. Moreover, as a water-soluble organic solvent, nitrogen-containing compounds other than these, saccharides, amines, etc. may be sufficient. Further, the pretreatment liquid may contain a water-soluble organic solvent that can be used in the textile printing ink composition described later.

  The pretreatment liquid may contain 1,2-alkanediol. When the pretreatment liquid contains 1,2-alkanediol, the penetrability of the pretreatment liquid into the fabric (to be printed) can be made appropriate. 1,2-alkanediol is a compound having a structure in which two hydroxyl groups (hydroxyl groups) are bonded to the 1st and 2nd carbons of one terminal of an alkane (hydrocarbon) having 3 or more carbon atoms. It is.

  1,2-alkanediol has a hydrophobic part composed of a hydrocarbon chain and a hydrophilic part formed by arranging two hydroxyl groups at the end of the hydrocarbon chain. The hydrocarbon chain may be linear or branched, but in the pretreatment liquid of the present embodiment, one in which two hydroxyl groups are arranged at the end of the linear hydrocarbon is preferable. .

Examples of such 1,2-alkanediol include 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2 -Carbon number of octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 1,2-tridecanediol, 1,2-tetradecanediol, etc. The 1,2-alkanediol of 3 or more and 14 or less is mentioned. Among these, in the pretreatment liquid of the present embodiment, the number of carbon atoms of 1,2-alkanediol is preferably 4 or more and 12 or less, from the viewpoint of not excessively reducing the permeability to the fabric and the interfacial tension. It is preferably 4 or more and 10 or less, more preferably 4 or more and 9 or less, and particularly preferably 6 or more and 9 or less.

  The pretreatment liquid may contain a plurality of the above-exemplified 1,2-alkanediols. The total content of 1,2-alkanediol with respect to the whole pretreatment liquid is 0.1 to 20% by mass, preferably 0.3 to 15% by mass, and more preferably 0.5% or more. It is 10 mass% or less, More preferably, it is 1 mass% or more and 7 mass% or less.

2.2.3. Resin emulsion The pretreatment liquid may contain a resin emulsion. By containing the resin emulsion, the fixing (fixing) property of the pigment contained in the ink composition to the fabric may be further improved. Further, the resin emulsion may function as a sealing agent that suppresses penetration of the pretreatment liquid and / or the ink composition into the fabric.

  Examples of such resin emulsions include, but are not limited to, at least one resin emulsion selected from urethane, styrene acrylic, acrylic, and vinyl chloride-vinyl acetate. In the pretreatment liquid, one or more of these resin emulsions can be used.

  The urethane resin emulsion is not particularly limited as long as it has a urethane bond in the molecule, but in addition to the urethane bond, a polyether type urethane resin emulsion containing an ether bond in the main chain, an ester bond in the main chain. Polyester-type urethane resin emulsions including polycarbonate-type urethane resin emulsions including a carbonate bond in the main chain can also be used. In addition, you may include the urethane type resin emulsion which has a crosslinkable group mix | blended with the textile printing ink composition mentioned later.

  The D50 of the resin particles in the resin emulsion is preferably 30 nm or more and 300 nm or less, and more preferably 40 nm or more and 100 nm or less. When D50 is within the above range, the resin emulsion particles can be uniformly dispersed in the pretreatment liquid. In addition, the rub resistance of the printed matter is further improved.

As commercial products of these resin emulsions,
Microgel E-1002, E-5002 (trade name, styrene-acrylic resin emulsion manufactured by Nippon Paint Co., Ltd.)
Boncoat 4001 (trade name, acrylic resin emulsion manufactured by DIC), Boncoat 5454 (trade name, manufactured by DIC, styrene-acrylic resin emulsion),
Polysol AM-710, AM-920, AM-2300, AP-4735, AT-860, PSASE-4210E (acrylic resin emulsion),
Polysol AP-7020 (styrene / acrylic resin emulsion),
Polysol SH-502 (vinyl acetate resin emulsion),
Polyzole AD-13, AD-2, AD-10, AD-96, AD-17, AD-70 (ethylene vinyl acetate resin emulsion),
Polysol PSASE-6010 (ethylene / vinyl acetate resin emulsion) (trade name, manufactured by Showa Denko KK),
Polysol SAE1014 (trade name, styrene-acrylic resin emulsion, manufactured by Zeon Corporation),
Cybinol SK-200 (trade name, acrylic resin emulsion, manufactured by Saiden Chemical Co., Ltd.),
AE-120A (trade name, acrylic resin emulsion manufactured by JSR),
AE373D (trade name, manufactured by Etec, carboxy-modified styrene / acrylic resin emulsion),
Seikadine 1900W (trade name, ethylene / vinyl acetate resin emulsion manufactured by Dainichi Seika Kogyo Co., Ltd.),
VINYBRAN 2682 (acrylic resin emulsion),
VINYBRAN 2886 (vinyl acetate / acrylic resin emulsion),
VINYBRAN 5202 (acetic acid acrylic resin emulsion) (trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Elitel KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, KT-0507 (trade name, manufactured by Unitika, polyester resin emulsion), Hitech SN-2002 (trade name, manufactured by Toho Chemical Co., polyester resin) Emulsion),
Takelac W-6020, W-635, W-6061, W-605, W-635, W-6021 (trade name, urethane resin emulsion, manufactured by Mitsui Chemicals Polyurethanes)
Superflex 870, 800, 150, 420, 460, 470, 610, 700 (trade name, urethane resin emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd.),
Permarin UA-150 (manufactured by Sanyo Chemical Industries, Ltd., urethane resin emulsion),
Suncure 2710 (Nippon Lubrizol, urethane resin emulsion),
NeoRez R-9660, R-9937, R-940 (Enomoto Kasei Co., Ltd., urethane resin emulsion),
Adekabon titer HUX-380,290K (made by ADEKA, urethane resin emulsion),
Mobile 966A, Mobile 7320 (manufactured by Nippon Synthetic Chemical Co., Ltd.),
Jonkrill 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (above, manufactured by BASF),
NK binder R-5HN (manufactured by Shin-Nakamura Chemical Co., Ltd.),
And Hydran WLS-210 (non-crosslinkable polyurethane: manufactured by DIC Corporation).

  When the pretreatment liquid contains a resin emulsion, the content of the resin emulsion in the pretreatment liquid in terms of solid content is preferably 1 to 20 when the total mass of the pretreatment liquid is 100% by mass. % By mass, more preferably 1.5 to 15% by mass, still more preferably 2 to 10% by mass. When the content of the resin emulsion in terms of solid content is within the above range, the washing durability of the image is further improved. The amount in terms of solid content refers to the amount excluding substances other than the resin (solid content) in the resin emulsion.

  In the case where a resin emulsion is included in the pretreatment liquid, and the resin emulsion is blended in the ink composition, both resin emulsions may be the same or different.

2.2.4. Surfactant The ink composition according to this embodiment may contain a surfactant. The surfactant may be any of nonionic surfactants, anionic surfactants, and amphoteric surfactants, whether or not the above cationic surfactants are employed. You may use together. The surfactant can reduce the interfacial tension of the pretreatment liquid and increase the permeability to the fabric.

  When a surfactant is added to the pretreatment liquid, the total amount of the surfactant is less than 0.5% by mass, preferably less than 0.1% by mass, and more preferably 0.05% with respect to the entire pretreatment liquid. Less than mass%, particularly preferably less than 0.01 mass% is preferable. In the pretreatment liquid, the surfactant is an optional component, and even if it is not contained, the function and action of the pretreatment liquid can be sufficiently exerted.

  As the nonionic surfactant, at least one of acetylene glycol surfactant, acetylene alcohol surfactant, fluorosurfactant, and polysiloxane surfactant is preferable. When the ink composition contains these surfactants, the wettability to the fabric and the dispersion stability of the pigment are further improved.

  Examples of the acetylene glycol surfactant and the acetylene alcohol surfactant include, but are not limited to, 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7. , 9-tetramethyl-5-decyne-4,7-diol alkylene oxide adduct, and 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol, Selected from alkylene oxide adducts of 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol, 2,4-dimethyl-5-hexyn-3-ol One or more types can be exemplified. Commercially available acetylene glycol surfactants and acetylene alcohol surfactants can also be used. Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA (all are trade names, manufactured by Air Products and Chemicals, Inc.), Olphin B, Y, P, A STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all trade names, Kawaken Fine Chemical Co., Ltd.).

  As the fluorosurfactant, commercially available ones may be used, and examples thereof include Megafac F-479 (manufactured by DIC Corporation), BYK-340 (manufactured by Big Chemie Japan), and the like.

  As the polyorganosiloxane-based surfactant, commercially available ones can be used. For example, Olfine PD-501, Olfine PD-502, Olfine PD-570 (all manufactured by Nissin Chemical Industry Co., Ltd.), BYK-347, BYK-348, BYK-302 (all are manufactured by Big Chemie Co., Ltd.) and the like.

  BYK-348 and BYK-302 are both siloxane-based surfactants (silicon-based surfactants), but when blended in the pretreatment liquid, BYK-302 has the ability to lower the interfacial tension. Since it is small, it can be used more suitably.

  Furthermore, examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkyl glucoside, polyoxyalkylene glycol alkyl ether, polyoxyalkylene glycol, polyoxyalkylene glycol alkyl phenyl ether, and sucrose fatty acid. Ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene acetylene glycol, polyoxyalkylene glycol alkylamine, polyoxyethylene alkylamine, polyoxyethylene alkylamine oxide, fatty acid alkanolamide, alkyl Roll amide, polyoxyethylene polyoxypropylene block It may also be used polymers, and the like.

Examples of the anionic surfactant include higher fatty acid salt, soap, α-sulfo fatty acid methyl ester salt, linear alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, monoalkyl phosphate ester salt, α -Olefin sulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonate, naphthalene sulfonate, alkane sulfonate, polyoxyethylene alkyl ether sulfate, sulfosuccinate, polyoxyalkylene glycol alkyl ether phosphate ester, etc. Is mentioned.

  Examples of amphoteric surfactants include alkylamino fatty acid salts as amino acids, alkylcarboxyl betaines as betaines, and alkylamine oxides as amine oxides. The amphoteric surfactant is not limited to these. A plurality of the surfactants may be used in combination.

2.2.5. Other Components The pretreatment liquid of this embodiment may be appropriately added with various additives such as chelating agents, preservatives, pH adjusters, viscosity adjusters, antioxidants, and antifungal agents as necessary. Can do.
Moreover, the pretreatment liquid of the present embodiment may further contain a polyvalent metal salt as long as the effects of the present invention are not impaired. The polyvalent metal compound is a compound containing a divalent or higher polyvalent metal ion and an anion. Examples of the divalent or higher polyvalent metal ions include Ca ²⁺ , Mg ²⁺ , Cu ²⁺ , Ni ²⁺ , Zn ²⁺ , Ba ²⁺ , and Al ³⁺ . Examples of the anion include Cl ⁻ , NO ³⁻ , CH ₃ COO ⁻ , I ⁻ , Br ⁻ , ClO ₃ ^{− and the} like. Among these, it is preferable to use a magnesium salt, a calcium salt, or an aluminum salt, which has a high aggregation effect. An example of the polyvalent metal salt is CaCl2.

2.3. Physical Properties of Pretreatment Liquid From the viewpoint of making the permeability to the fabric appropriate, the pretreatment liquid according to this embodiment has a surface tension at 25 ° C. of 30 mN / m or more, preferably 35 mN / m or more, more preferably. Is preferably 38 mN / m or more, more preferably 40 mN / m or more. The surface tension is measured by using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) by confirming the surface tension when the platinum plate is wetted with the composition in an environment of 25 ° C. can do.

  In addition, the pretreatment liquid may be attached to the fabric by an inkjet method, and in that case, the viscosity at 20 ° C. is preferably 1.5 mPa · s to 15 mPa · s. It is more preferably 5 mPa · s or more and 5 mPa · s or less, and more preferably 1.5 mPa · s or more and 3.6 mPa · s or less.

  On the other hand, the pretreatment liquid may be performed by a method other than the ink jet method. Examples of such a method include a method of applying the pretreatment liquid to the fabric using various sprays, a method of applying the cloth by immersing the fabric in the pretreatment liquid, and a method of applying the treatment liquid to the fabric with a brush or the like. One of the contact method and the contact method, or a combination thereof is mentioned.

  When the pretreatment liquid is attached to the fabric by a method other than the ink jet method, the viscosity at 20 ° C. may be higher than that by the ink jet method, for example, 1.5 mPa · s or more and 100 mPa · s. Hereinafter, it is preferably 1.5 mPa · s or more and 50 mPa · s or less, more preferably 1.5 mPa · s or more and 20 mPa · s or less. The viscosity is measured by using a viscoelasticity tester MCR-300 (manufactured by Pysica), increasing the Shear Rate to 10 to 1000 in an environment of 20 ° C., and reading the viscosity at Shear Rate 200. Can be measured.

3. Textile ink composition In the textile printing method of this embodiment, the pretreatment liquid of this embodiment described above is attached to the fabric, and then the textile printing ink composition is attached to the fabric by the ink jet method. Hereinafter, the textile printing ink composition will be described.

3.1. Urethane Resin Having Crosslinkable Group The printing ink composition of the present embodiment contains a urethane resin having a crosslinkable group. Crosslinkable groups (isocyanate groups) are chemically protected (capping or blocking) and are deprotected and activated by the application of heat to form bonds (eg, urethane bonds, urea bonds, allophanate bonds, etc.). Will do.

  Moreover, since three or more crosslinkable groups of the urethane-based resin having a crosslinkable group are provided in one molecule, a crosslinked structure is formed by the reaction of the crosslinkable group. In this specification, the urethane resin is a urethane bond or urea bond formed by reacting an isocyanate group with another reactive group (for example, a hydroxyl group, an amino group, a urethane bond group, a carboxyl group, etc.). It refers to a resin containing an allophanate bond or the like. Therefore, in this specification, for example, urea resin is included in urethane resin.

  Blocked isocyanates (chemically protected isocyanates) contain latent isocyanate groups whose isocyanate groups are blocked by a blocking agent and can be obtained, for example, by reacting a polyisocyanate compound with a blocking agent. .

  Examples of the polyisocyanate compound include polyisocyanate monomers and polyisocyanate derivatives. Examples of the polyisocyanate monomer include polyisocyanates such as aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyisocyanate monomers can be used alone or in combination of two or more.

  Examples of the polyisocyanate derivative include a multimer (for example, dimer, trimer (for example, isocyanurate-modified product, iminooxadiazinedione-modified product), pentamer, 7) of the polyisocyanate monomer described above. ), Allophanate-modified products (for example, allophanate-modified products produced from the reaction of the above-described polyisocyanate monomer and a low molecular weight polyol described below), polyol-modified products (for example, polyisocyanate monomer and below-mentioned). Polyol modified products (alcohol adducts, etc.) produced by reaction with low molecular weight polyols, biuret modified products (for example, biuret modified products produced by reaction of the above polyisocyanate monomer with water or amines, etc.) ), Modified urea (for example, the above-mentioned polyisocyanate monomer and diamine) Urea-modified products produced by the reaction), oxadiazine trione-modified products (for example, oxadiazine trione produced by the reaction of the above-mentioned polyisocyanate monomer and carbon dioxide gas), carbodiimide-modified products (the above-mentioned polyisocyanate). Carbodiimide modified products produced by decarboxylation condensation reaction of monomers), uretdione modified products, uretonimine modified products, and the like.

  When two or more polyisocyanate compounds are used in combination, for example, at the time of production of blocked isocyanate, two or more polyisocyanate compounds may be reacted simultaneously, and each polyisocyanate compound is used individually. You may mix the blocked isocyanate obtained by this.

  The blocking agent blocks the isocyanate group to inactivate it, but regenerates or activates the isocyanate group after deblocking, and activates the isocyanate group in the blocked and deblocked state of the isocyanate group. It also has a catalytic action.

  Blocking agents include imidazole compounds, imidazoline compounds, pyrimidine compounds, guanidine compounds, alcohol compounds, phenol compounds, active methylene compounds, amine compounds, imine compounds, oxime compounds, carbamic acid compounds. , Urea compounds, acid amide (lactam) compounds, acid imide compounds, triazole compounds, pyrazole compounds, mercaptan compounds, bisulfites and the like.

  Examples of the imidazole compound include imidazole (dissociation temperature 100 ° C.), benzimidazole (dissociation temperature 120 ° C.), 2-methylimidazole (dissociation temperature 70 ° C.), 4-methylimidazole (dissociation temperature 100 ° C.), 2-ethyl. Examples include imidazole (dissociation temperature 70 ° C.), 2-isopropylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, and the like.

  Examples of the imidazoline-based compound include 2-methylimidazoline (dissociation temperature 110 ° C.), 2-phenylimidazoline, and the like.

  Examples of pyrimidine compounds include 2-methyl-1,4,5,6-tetrahydropyrimidine.

  Examples of the guanidine compound include 3,3-dialkylguanidines such as 3,3-dimethylguanidine, for example, 1,1,3, such as 1,1,3,3-tetramethylguanidine (dissociation temperature 120 ° C.). 3-tetraalkyl guanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene and the like can be mentioned.

  Examples of the alcohol compound include methanol, ethanol, 2-propanol, n-butanol, s-butanol, 2-ethylhexyl alcohol, 1- or 2-octanol, cyclohexyl alcohol, ethylene glycol, benzyl alcohol, 2,2 , 2-trifluoroethanol, 2,2,2-trichloroethanol, 2- (hydroxymethyl) furan, 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-ethoxy Ethoxyethanol, 2-ethoxybutoxyethanol, butoxyethoxyethanol, 2-butoxyethylethanol, 2-butoxyethoxyethanol, N, N-dibutyl-2-hydroxyacetamide, N-hydro Cysuccinimide, N-morpholine ethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine (dissociation temperature 140 ° C.), furfuryl alcohol, 12-hydroxystearic acid , Triphenylsilanol, 2-hydroxyethyl methacrylate and the like.

Examples of phenolic compounds include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, s-butylphenol, t-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n -Nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-s-butylphenol, di-t-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-n -Nonylphenol, nitrophenol, bromophenol, chlorophenol, fluorophenol, dimethylphenol, styrenated phenol, methyl salicyla , Methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl hydroxybenzoate, 4-[(dimethylamino) methyl] phenol, 4-[(dimethylamino) methyl] nonylphenol, bis (4-hydroxy Phenyl) acetic acid, 2-hydroxypyridine (dissociation temperature 80 ° C.), 2- or 8-hydroxyquinoline, 2-chloro-3-pyridinol, pyridine-2-thiol (dissociation temperature 70 ° C.), and the like.

  Examples of the active methylene compound include Meldrum's acid, dialkyl malonate (for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-t-butyl malonate, di-2-ethylhexyl malonate, malonic acid. Methyl n-butyl, ethyl n-butyl malonate, methyl s-butyl malonate, ethyl s-butyl malonate, methyl t-butyl malonate, ethyl t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, malon Diphenyl acid, benzyl methyl malonate, ethyl phenyl malonate, t-butylphenyl malonate, isopropylidene malonate, etc.), alkyl acetoacetate (eg methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate) , N-butyl acetoacetate, acetoacetic acid - butyl acetoacetate benzyl, acetoacetic acid phenyl), 2-acetoacetoxyethyl methacrylate, acetylacetone, and the like cyanoethyl acetate.

  Examples of the amine compound include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis (2,2,6,6-tetramethylpiperidinyl) amine, di-n-propylamine, diisopropylamine ( Dissociation temperature 130 ° C), isopropylethylamine, 2,2,4- or 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine (dissociation temperature 140 ° C), dicyclohexylamine (dissociation temperature 130 ° C), Bis (3,5,5-trimethylcyclohexyl) amine, piperidine, 2,6-dimethylpiperidine (dissociation temperature 130 ° C), t-butylmethylamine, t-butylethylamine (dissociation temperature 120 ° C), t-butylpropylamine , T-butylbutylamine, t-butyl Nylamine (dissociation temperature 120 ° C.), t-butylphenylamine, 2,2,6-trimethylpiperidine, 2,2,6,6-tetramethylpiperidine (dissociation temperature 80 ° C.), (dimethylamino) -2,2, Examples include 6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6-methyl-2-piperidine, and 6-aminocaproic acid.

  Examples of the imine compound include ethyleneimine, polyethyleneimine, 1,4,5,6-tetrahydropyrimidine, guanidine and the like.

  Examples of oxime compounds include formaldoxime, acetoaldoxime, acetoxime, methylethylketoxime (dissociation temperature 130 ° C.), cyclohexanone oxime, diacetylmonooxime, benzophenoxime, 2,2,6,6-tetramethyl. Cyclohexanone oxime, diisopropyl ketone oxime, methyl t-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethyl heptyl ketone oxime, methyl isoamyl ketone Oxime, n-amyl ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4'-dimethoxybenzofe N'okishimu, 2-cycloheptanone oxime and the like.

  Examples of the carbamic acid compound include phenyl N-phenylcarbamate.

  Examples of the urea compound include urea, thiourea, and ethylene urea.

  Examples of acid amide (lactam) compounds include acetanilide, N-methylacetamide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, laurolactam, and the like. It is done.

  Examples of the acid imide compound include succinimide, maleic imide, phthalimide, and the like.

  Examples of triazole compounds include 1,2,4-triazole and benzotriazole.

  Examples of the pyrazole compound include pyrazole, 3,5-dimethylpyrazole (dissociation temperature 120 ° C.), 3,5-diisopropylpyrazole, 3,5-diphenylpyrazole, 3,5-di-t-butylpyrazole, 3- Examples include methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole.

  Examples of mercaptan compounds include butyl mercaptan, dodecyl mercaptan, hexyl mercaptan, and the like.

  Examples of the bisulfite include sodium bisulfite.

  Further, the blocking agent is not limited to the above, and examples thereof include other blocking agents such as benzoxazolone, isatoic anhydride, tetrabutylphosphonium acetate, and the like.

  In addition, about some compounds illustrated above, dissociation temperature was written together as temperature which reproduces | regenerates an isocyanate group.

  Such blocking agents can be used alone or in combination of two or more. The dissociation temperature of the blocking agent can be appropriately selected. The dissociation temperature is, for example, 60 ° C. or higher and 230 ° C. or lower, preferably 80 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 180 ° C. or lower, and further preferably 110 ° C. or higher and 160 ° C. or lower. Within such a temperature range, the pot life of the textile printing ink composition can be made sufficiently long, and the temperature in the heating step can be prevented from becoming too high.

  The main chain of the urethane resin having a crosslinkable group may be any of a polyether type including an ether bond, a polyester type including an ester bond, a polycarbonate type including a carbonate bond, and the like. When the urethane-based resin having a crosslinkable group is crosslinked (crosslinked product), the elongation at break and 100% modulus can be adjusted by changing the density of the crosslinking points and the kind of the main chain. . Among these, the urethane resin having a crosslinkable group having a polycarbonate skeleton or a polyether skeleton has a good balance between elongation at break and 100% modulus, frictional durability of images, and printed matter. It is more preferable because it is easy to improve the texture.

  In addition, the urethane-based resin having a crosslinkable group has an elongation at break of 150% or more, preferably 170% or more, more preferably 200% or more, and still more preferably, after crosslinking is formed (crosslinked product). , 300% or more is preferable. By selecting the density of the cross-linking points and the type of the main chain so as to obtain such an elongation at break, the texture of the printed material can be improved.

Here, the elongation at break is, for example, by curing a urethane resin emulsion having a crosslinkable group to prepare a film having a thickness of about 60 μm, under the conditions of a tensile test gauge length of 20 mm and a pulling speed of 100 mm / min. The value obtained by measuring with can be adopted. 10
As the 0% modulus, a value obtained by measuring the tensile stress when the film is stretched 100% with respect to the original length in the tensile test can be adopted. The film to be measured may be formed using a urethane resin emulsion having a crosslinkable group, or may be formed by molding using the same kind of resin, but is preferably formed using an emulsion resin.
The urethane resin having a crosslinkable group may be blended in the form of an emulsion. Such a resin emulsion is a so-called self-reactive urethane resin emulsion, and a commercially available urethane resin emulsion having an isocyanate group blocked with a blocking agent having a hydrophilic group can be used.

As a commercial product of urethane-based resin having a crosslinkable group,
Takelac WS-6021 (trade name, urethane-based resin emulsion, polyether-based polyurethane having a polyether-derived skeleton, manufactured by Mitsui Chemicals Polyurethane),
WS-5100 (trade name, urethane-based resin emulsion, polycarbonate-based polyurethane having a polycarbonate-derived skeleton, manufactured by Mitsui Chemicals Polyurethanes),
Elastron E-37, H-3 (the above is a polyester polyurethane whose main chain has a polyester-derived skeleton),
Elastron H-38, BAP, C-52, F-29, W-11P (the above is a polyether polyurethane having a main chain having a polyether-derived skeleton) (trade name, urethane resin emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ,
Superflex 870, 800, 150, 420, 460, 470, 610, 700 (trade name, urethane resin emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd.),
Permarin UA-150 (manufactured by Sanyo Chemical Industries, Ltd., urethane resin emulsion),
Suncure 2710 (Nippon Lubrizol, urethane resin emulsion),
NeoRez R-9660, R-9937, R-940 (Enomoto Kasei Co., Ltd., urethane resin emulsion),
Adekabon titer HUX-380,290K (manufactured by ADEKA Corporation, urethane resin emulsion), and the like can be exemplified.

  These urethane resins may be contained in the pretreatment agent. In that case, the urethane resin contained in the pretreatment agent and the urethane resin contained in the printing ink composition may be the same. May be different.

  In addition, the temperature of the heating step of the inkjet printing method of the present embodiment is such that at least a part of the crosslinkable group is in consideration of the deprotection temperature (dissociation temperature) of the isocyanate group of the urethane resin having the crosslinkable group. Set to activate.

3.2. Other components 3.2.1. Pigment The textile printing ink composition of the present embodiment may contain a pigment. When the pigment is attached to the fabric, the fabric is printed and a printed product (printed product) is formed.

The pigment is not particularly limited, and any of inorganic pigments and organic pigments can be used. Examples of the pigment include organic pigments such as azo, phthalocyanine, condensed polycyclic, nitro, nitroso, hollow resin particles, and polymer particles (brilliant carmine 6B, lake red C, watching red, disazo yellow, hansa). Yellow, phthalocyanine blue, phthalocyanine green, alkali blue, aniline black, etc.); metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, nickel, titanium oxide, zinc oxide, antimony oxide, Metal oxides and sulfides such as zinc sulfide and zirconium oxide, and carbon blacks (CI pigment black 7) such as furnace carbon black, lamp black, acetylene black, and channel black, as well as loess, ultramarine blue, And bitumen etc. It can be used as the inorganic pigment.

As carbon black used as a black pigment, 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B etc. (above, manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven
1255, Raven 700, etc. (above, manufactured by Columbia Carbon Co., Ltd.), Rega1 400R, Rega1 330R, Rega1 660R, Mogu L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1100, Monarch 1100, Monarch 1100 (Above, manufactured by Cabot), Color
Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5 , Special Black 4A, Special Black 4 (manufactured by Degussa) and the like.

  Examples of white pigments include C.I. I. Pigment White 1 (basic lead carbonate), 4 (zinc oxide), 5 (mixture of zinc sulfide and barium sulfate), 6 (titanium oxide), 6: 1 (titanium oxide containing other metal oxides), 7 (Zinc sulfide), 18 (calcium carbonate), 19 (clay), 20 (titanium mica), 21 (barium sulfate), 22 (natural barium sulfate), 23 (gloss white), 24 (alumina white), 25 (gypsum) ), 26 (magnesium oxide / silicon oxide), 27 (silica), 28 (anhydrous calcium silicate), and the like.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, 180 and the like.

  Examples of magenta pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, and C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.

  Examples of cyan pigments include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, and C.I. I. Bat Blue 4, 60 and the like.

  Examples of pigments other than black, white, yellow, magenta and cyan include C.I. I. Pigment green 7, 10, and C.I. I. Pigment brown 3, 5, 25, 26, and C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63 and the like.

  These exemplified pigments may be used as a mixture of plural kinds. The total content of the pigment (solid content) in the printing ink composition varies depending on the pigment type used, but from the viewpoint of obtaining good color development, the total mass of the printing ink composition is 100% by mass. The content is preferably 1 to 30% by mass, more preferably 2 to 15% by mass.

  In preparing the textile printing ink composition, a pigment dispersion liquid in which a pigment is dispersed in advance may be prepared, and the pigment dispersion liquid may be added to the textile printing ink composition. As a method for obtaining such a pigment dispersion, a method of dispersing a self-dispersed pigment in a dispersion medium without using a dispersant, a method of dispersing a pigment in a dispersion medium using a polymer dispersant, and a surface treatment are performed. There is a method of dispersing a pigment in a dispersion medium.

  Also, when pigment printing is performed with a white (white) pigment, such as when a colored fabric is printed, there is a strong tendency for color development to be insufficient (whiteness is insufficient). However, when the textile printing ink composition of the present embodiment is a white textile ink composition using a white pigment, it is very difficult to produce a printed article because of the effect of suppressing the permeability by the pretreatment liquid and the effect of pigment aggregation. Excellent color developability can be achieved.

3.2.2. Water The textile printing ink composition of this embodiment may contain water. The water is the same as described in the above pretreatment liquid. The water content is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more with respect to the total amount of the textile printing ink composition. The water in the textile printing ink composition includes, for example, a pigment dispersion used as a raw material, a resin particle dispersion, and water to be added. When the water content is 30% by mass or more, the textile printing ink composition can have a relatively low viscosity. Further, the upper limit of the water content is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less, with respect to the total amount of the textile printing ink composition. In the present specification, the expression “water-based ink” or the like refers to an ink containing 30% by mass or more of water with respect to the total mass (100% by mass) of the ink.

3.2.3. Water-soluble organic solvent The ink composition of the present embodiment may contain a water-soluble organic solvent. By including the water-soluble organic solvent, it is possible to effectively suppress the evaporation of moisture from the recording head when the ink composition is left standing for a long time while improving the ejection stability of the ink composition by the ink jet method.

  Examples of the water-soluble organic solvent include polyol compounds, glycol ethers, betaine compounds, and the like.

Examples of the polyol compound include a polyol compound (preferably a diol compound) having 2 to 6 carbon atoms in the molecule and having one ether bond in the molecule. Specific examples include diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, methyl triglycol (triethylene glycol monomethyl ether), butyl triglycol (Triethylene glycol monobutyl ether), butyl diglycol (diethylene glycol monobutyl ether), dipropylene glycol monopropyl ether, glycerin, 1,2-hexanediol, 1,2-heptanediol, 1,3-propanediol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl -3-phenoxy-1,2-propanediol, 3- (3-methylphenoxy) -1,2-propanediol, 3-hexyloxy-1,2-propanediol, 2-hydroxymethyl-2-phenoxymethyl- 1,3-propanediol, 3-methyl-1,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,4-butanediol, 1,5- Examples include glycols such as pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, and 3-methyl-1,5-pentanediol.

  Examples of glycol ethers include monoalkyl ethers of glycols selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol. preferable. More preferably, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monopropyl ether and the like can be mentioned.

  A betaine compound is a compound that has a positive charge and a negative charge at non-adjacent positions in the same molecule, and has no positively charged hydrogen atoms bonded to dissociable hydrogen atoms, so that the molecule as a whole has no charge. (Inner salt). Preferred betaine compounds are N-alkyl substituted amino acids, more preferably N-trialkyl substituted amino acids. Examples of the betaine compound include trimethylglycine (also referred to as “glycine betaine”), γ-butyrobetaine, homarine, trigonelline, carnitine, homoserine betaine, valine betaine, lysine betaine, ornithine betaine, alanine betaine, stachydrine, and glutamic acid betaine. Preferably, a trimethylglycine etc. can be illustrated.

  A pyrrolidone derivative may be used as the water-soluble organic solvent. Examples of pyrrolidone derivatives include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone. Etc.

  A plurality of water-soluble organic solvents may be used in combination. The total amount of the water-soluble organic solvent is 0.2% by mass or more and 30% in total with respect to the total amount of the printing ink composition from the viewpoint of adjusting the viscosity of the printing ink composition and preventing clogging due to the moisturizing effect. % By mass or less, preferably 0.4% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and further preferably 0.7% by mass or more and 10% by mass or less.

3.2.4. Surfactant The ink composition of the present embodiment may contain a surfactant. As the surfactant, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, and these may be used in combination. The surfactant can reduce the interfacial tension of the ink composition and increase the permeability to the fabric. Specific examples of the surfactant are the same as those described in the section of the pretreatment liquid. However, since the cationic surfactant may aggregate the components of the textile printing ink composition, it is more preferable to use a small amount of surfactant or another type of surfactant.

  When a surfactant is added to the printing ink composition, the total amount of the surfactant is 0.01% by mass or more and 3% by mass or less, preferably 0.05% by mass or more and 2%, based on the entire printing ink composition. It is preferable to blend it by mass% or less, more preferably 0.1 mass% or more and 1 mass% or less, particularly preferably 0.2 mass% or more and 0.5 mass% or less.

When the textile printing ink composition contains a surfactant, the stability when ejecting ink from the head tends to increase. In addition, the use of an appropriate amount of the surfactant improves the permeability to the fabric and can increase the contact with the pretreatment liquid. Thereby, the aggregation of the pigment and the thickening of the printing ink composition are likely to occur, and the color development of the printed product can be further improved. When a surfactant is added to the ink in excess of an appropriate amount, the excess surfactant may bleed out after printing, and the fastness of the printed image may be insufficient.

3.2.5. Chelating agent The printing ink composition of the present embodiment may contain a chelating agent. Chelating agents have the property of trapping ions. Examples of such a chelating agent include ethylenediaminetetraacetate (EDTA), ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, and metaphosphate.

3.2.6. Preservative The textile printing ink composition of the present embodiment may contain a preservative. By containing a preservative, the growth of mold and bacteria can be suppressed, and the storage stability of the ink composition becomes better. As a result, for example, the textile ink composition can be easily used as a maintenance liquid for maintenance without using a printer for a long period of time. Preferable examples of the preservative include proxel CRL, proxel BDN, proxel GXL, proxel XL-2, proxel IB, and proxel TN.

3.2.7. pH adjuster The textile printing ink composition of this embodiment may contain a pH adjuster. By containing the pH adjuster, for example, the elution of impurities from the member that forms the ink flow path can be suppressed or promoted, and the cleaning property of the textile printing ink composition can be adjusted. Examples of the pH adjusting agent include morpholines, piperazines, amino alcohols such as triethanolamine.

3.2.8. Other Components The textile printing ink composition according to this embodiment may contain the resin emulsion (such as a urethane-based resin having no crosslinkable group) described in the above section “2.2.3. Resin emulsion”. Furthermore, various additives such as a humectant, a viscosity modifier, a dissolution aid, an antioxidant, and an antifungal agent can be appropriately contained.

3.3. Physical properties of textile printing ink composition The textile printing ink composition according to this embodiment is applied to a fabric by an ink jet method. For this reason, the textile printing ink composition preferably has a surface tension at 25 ° C. of 10 mN / m or more and 40 mN / m or less from the viewpoint of the balance between the recording quality and the reliability as an ink for ink jet recording. More preferably, it is 40 mN / m or less.

  From the same viewpoint, the viscosity of the textile printing ink composition at 20 ° C. is preferably 2 mPa · s or more and 15 mPa · s or less, more preferably 2 mPa · s or more and 5 mPa · s or less, and 2 mPa · s or less. More preferably, it is 3.6 mPa · s or less.

4). Ink set The ink set for inkjet printing according to this embodiment includes a pretreatment liquid containing a cationic organic compound and a printing ink composition containing a urethane resin having a crosslinkable group. Such pretreatment liquid and textile printing ink composition are as described above, and detailed description thereof is omitted.

  According to the ink set of the loss embodiment, the cationic organic compound contained in the pretreatment liquid causes the coloring material contained in the printing ink composition to remain in the vicinity of the surface of the fabric (printing target) and has sufficient color development. An image (printed product) can be obtained, and when the urethane resin having a crosslinkable group is crosslinked, the fabric is entangled with the cationic organic compound, and the entanglement between the cationic organic compound and the crosslinked urethane resin. , Etc. can be caused to occur, so that the coloring material can be sufficiently fixed to the fabric, and an image (printed product) having good fastness can be obtained.

5. Examples and Comparative Examples Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

5.1. Preparation of pretreatment liquid Each component was put in a container so as to have the composition shown in Table 1, and mixed and stirred for 2 hours with a magnetic stirrer and mixed well. After stirring for 1 hour, each pretreatment liquid was obtained by filtering using a 5 μm PTFE membrane filter. The numerical values in Table 1 indicate mass%, and pure water (ion exchange water) was added so that the mass of each pretreatment liquid was 100 mass%.

  Moreover, what was described in Table 1 was also used about the cationic organic compound. Table 1 shows the mass% of the cationic organic compound. That is, although the emulsion was used for preparation of the pretreatment liquid, the solid content was converted and listed in Table 1.

5.2. Resins used for printing ink compositions Table 2 shows the resins used for the printing ink compositions used in Examples and Comparative Examples. Note that Takelac WS-6021 and Takelac WS-5100 are urethane resins having a self-crosslinkable crosslinkable group manufactured by Mitsui Chemicals, Inc., and Elastron E-37 is a self-crosslinkable crosslinkable group manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Hydran WLS-210 is a urethane-based resin (polycarbonate) that does not have a self-crosslinkable crosslinking group manufactured by DIC Corporation, and Mobile 966A is a self-crosslinked product manufactured by Nippon Synthetic Chemical Co., Ltd. It is an acrylic resin having a functional crosslinking group.

Table 2 shows the elongation at break and the value of 100% modulus of each resin. In addition,
The elongation at break was measured using a resin emulsion of about 60 μm in thickness, heated at 170 ° C. for 5 minutes, and then measured under conditions of a tensile test gauge length of 20 mm and a pulling speed of 100 mm / min. The value obtained was adopted. For the 100% modulus, the value obtained by measuring the tensile stress when the film was stretched 100% with respect to the original length in the tensile test was adopted.

5.3. Preparation of textile printing ink composition Each component was put into a container so as to have the composition shown in Table 3 and Table 4, mixed and stirred with a magnetic stirrer for 2 hours, and further filled with zirconia beads having a diameter of 0.3 mm. The mixture was sufficiently mixed by carrying out a dispersion treatment at. After stirring for 1 hour, each textile printing ink composition was obtained by filtering using a 5 μm PTFE membrane filter. The numerical values in Table 1 indicate mass%, and pure water (ion exchange water) was added so that the mass of each printing ink composition was 100 mass%. Tables 3 and 4 show the No. of the pretreatment liquid used in each example and each comparative example. Was described.

In Tables 3 and 4, the cyan pigment dispersion is C.I. I. CI Pigment Blue 15: 3, 65 parts by 35 parts Jonkrill 611 (trade name: manufactured by BASF Japan Ltd.), 1.70 parts potassium hydroxide, ion exchange method and reverse osmosis method 250 parts of purified ultrapure water is mixed, dispersed for 10 hours in a ball mill with zirconia beads, filtered through glass fiber filter paper GA-100 (trade name: manufactured by Advantech Toyo Co., Ltd.) to remove coarse particles, and the pigment concentration (The weight percentage of the cyan pigment dispersion is described in Table 1 so that the concentration of the cyan pigment in the textile printing ink composition is 4.5% by weight.) .) BYK-348 is a siloxane-based surfactant manufactured by Big Chemie Japan. In addition, the components described by the compound names were all purchased as reagents.

5.4. Evaluation test 5.4.1. Preparation of printed matter The pretreatment liquid of each Example and each Comparative Example (excluding Comparative Example 6) described in Tables 3 and 4 was sufficiently contained in a sponge roller, and the roller was added to a fabric (Print Star Heavy). The weight (white) (5.6 oz) was rolled up and down and left and right three to four times, and the pretreatment liquid was applied as uniformly as possible. In Tables 3 and 4, a plurality of pretreatment liquids were used by mixing a plurality of pretreatment liquids at an equal ratio (Example 17).

  The coating amount was about 20 g per area of A4 size. The fabric coated with the pretreatment liquid was dried by heat treatment at 165 ° C. for 45 seconds using a heat press.

Using a printer (SC-F200) manufactured by Seiko Epson Corporation, the dried fabric was printed at a resolution of 1440 dpi × 1440 dpi and a coating amount of 200 mg / inch ² using each printing ink composition. After the printing, heat treatment at 165 ° C. for 5 minutes was performed again in a conveyor oven (hot air drying method) to fix the printed material.

5.4.2. Friction fastness test A dye fastness test against friction was carried out on each printed matter according to the method prescribed in ISO-105 X12 using a type I (clock meter) tester. Dry friction was tested in accordance with the dry test specified in ISO-105 X12, and wet friction was tested in accordance with the wet test specified in ISO-105 X12, and evaluated using a contaminated gray scale. The evaluation criteria are as follows, and the results are shown in Tables 3 and 4.
Dry friction fastness ◎: Friction fastness is 4th grade or better ○: Friction fastness is 3rd grade or higher and lower than 4th grade Δ: Friction fastness is 2nd grade or higher and lower than 3rd grade ×: Friction fastness is 2 Wet friction fastness that is less than grade A: Friction fastness is grade 3 or higher B: Friction fastness is grade 2 or higher and lower than grade Δ: Friction fastness is grade 1 or higher and lower than grade 2 x: Friction Fastness is less than 1st grade

5.4.3. Evaluation of color development The OD value of the printed material of each example was measured with a colorimeter (trade name “Gretag Macbeth Spectrolino”, manufactured by X-RITE), and based on the obtained OD value, the following evaluation criteria were used. The color developability was evaluated, and the results are shown in Tables 3 and 4.
◎: OD value is 1.45 or more ◯: OD value is 1.40 or more and less than 1.45 Δ: OD value is 1.30 or more and less than 1.45 ×: OD value is less than 1.30 Is

5.4.4. Evaluation of the texture of the printed material The printed portion of each printed material was directly touched with the palm of the hand, and the touch at that time was determined according to the following criteria. The decision was made by three people, and the opinion with the most support was taken as the result of the decision. When the judgment was divided into one by one, the opinion that was in between them was taken as the judgment result and listed in Tables 3 and 4.
A: The hardness and feel of the printed part are almost the same as the original fabric, and are good. ○: The hardness or the touch of the printed part is slightly changed compared to the original fabric, but there is no problem in practical use. Although the hardness or feel of the printed part is worse than that of the original fabric, it is within the allowable range. X: The printed part becomes hard and the feeling of use is poor and cannot be used practically.

5.5. Evaluation Results No. 1 containing a cationic polymer (PAA-HCL-3L, PAS-H-1L) or a cationic surfactant (Cathogen TML) as the cationic organic compound. Resin A (Takelac WS-6021), Resin B (WS-5100), and Resin C (Elastron E-37), which are urethane resins having a crosslinkable group, are used. All of the printed products of Examples had excellent results in fastness to friction and color development.

On the other hand, the printed matter of Comparative Example 1 using the resin D having no crosslinkability, and the printed matter of Comparative Example 2 using the acrylic resin (resin E) having crosslinkability are friction fastness. Was insufficient. In addition, the printed matter of Comparative Examples 3 and 4 containing a polyvalent metal salt (CaCl ₂ ) as a cationic substance in the pretreatment liquid also has insufficient fastness, particularly insufficient wet friction fastness. It was. This is thought to be due to the fact that polyvalent metal salts are easily soluble in water. Further, the printed matter of Comparative Example 5 using a pretreatment liquid containing no acetic acid and not containing a cationic organic compound, and the printed matter of Comparative Example 6 which was not subjected to pretreatment had insufficient color development. . This is presumably because the ability to aggregate the components of the textile printing ink composition was insufficient.

  On the other hand, when each example was compared, in the texture evaluation, when the resin concentration was high, or when a resin having a high 100% modulus and a low elongation at break was used, the texture tended to be slightly worse. .

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that exhibits the same operational effects as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (6)

For a fabric treated with a pretreatment liquid containing a cationic organic compound,
A printing ink composition containing a urethane-based resin having a crosslinkable group is attached;
An ink-jet printing method performed by heating the fabric. In claim 1,
The ink-jet printing method, wherein the textile printing ink composition further contains a pigment. In claim 1 or claim 2,
The inkjet printing method, wherein the cationic organic compound is at least one of a cationic polymer and a cationic surfactant. In any one of Claims 1 to 3,
The inkjet printing method, wherein the urethane resin has a polycarbonate skeleton or a polyether skeleton. In any one of Claims 1 thru | or 4,
The urethane-based resin has an elongation at break of 170% or more. A pretreatment liquid containing a cationic organic compound;
A printing ink composition containing a urethane-based resin having a crosslinkable group; and
Ink set for inkjet textile printing.