JP7411324B2 - Pretreatment liquid for textile printing, ink set for inkjet textile printing, and method for producing printed products - Google Patents

Description

Embodiments of the present invention relate to a pretreatment liquid for textile printing, an ink set for inkjet textile printing, and a method for producing a printed article using the same.

The inkjet method allows variable printing in a non-contact manner and is suitable for small-lot printing on various substrates. Among these, the inkjet method is generally suitable for fabrics because contact printing tends to cause wrinkles.

Fabrics have high ink absorbency and pigments do not easily remain on the surface of the fabric, so inkjet printing methods using pigment inks tend to result in poor color development. As a method for improving color development, Patent Document 1 discloses a means for increasing the image density of printed matter by applying a treatment liquid containing a cationic polymer before printing. Patent Document 2 discloses a means for containing polyvalent metal ions in a pretreatment liquid. However, it is presumed that the wet rubbing fastness is insufficient by these means.

Japanese Patent Application Publication No. 2011-168912 Japanese Patent Application Publication No. 2003-55886

SUMMARY OF THE INVENTION Therefore, one object of the present invention is to provide a pretreatment liquid for textile printing, an ink set for inkjet textile printing, and an ink set for inkjet textile printing that suppresses image bleeding and has high wet abrasion fastness in an inkjet textile printing method using pigment ink. An object of the present invention is to provide a method for producing a printed matter (printed material) using the present invention.

According to an embodiment of the present invention, there is provided a pretreatment liquid used with an inkjet ink containing at least a pigment and water, the pretreatment liquid containing 1 to 20% by mass of a polysaccharide having an amino group and an organic acid. A pretreatment liquid for textile printing is provided, which is characterized in that it contains 1 to 50% by mass of. According to another embodiment of the present invention, there is provided an ink set for inkjet textile printing, which includes the above-mentioned pretreatment liquid for textile printing and an ink for inkjet textile printing containing at least a pigment and water. According to another embodiment of the present invention, there is provided a method for manufacturing a printed article using the above-mentioned textile pre-treatment liquid, comprising ejecting an ink containing at least a pigment and water from an inkjet head to record an image on a fabric. Provided is a method for producing a printed article, which is characterized by the following.

According to embodiments of the present invention, there is provided a pre-treatment liquid for textile printing, an ink set for inkjet textile printing, and a printed article using the same, which can suppress image bleeding and produce printed printed matter with high wet abrasion fastness. A manufacturing method can be provided.

Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

[Pretreatment liquid for textile printing] The pretreatment liquid for textile printing according to one embodiment of the present invention contains 1 to 20% by mass of a polysaccharide having an amino group and 1 to 50% by mass of an organic acid. Hereinafter, the "textile printing pretreatment liquid" may be simply referred to as "pretreatment liquid." Further, "polysaccharide having an amino group" may be simply referred to as "polysaccharide".

This pretreatment liquid can be preferably used for textile printing.

By including a polysaccharide having an amino group in the pretreatment liquid, the wet rubbing fastness can be improved. It is thought that when a polysaccharide having an amino group is dissolved in water, the amino group becomes ammonium and becomes a polycation, which is adsorbed on the surface of an anionic pigment. By drying the pre-treatment liquid while adsorbing the pigment and forming a polysaccharide film, the polysaccharide becomes a binder, improving the fixation of the pigment to the fabric, and preventing the pigment from falling off the fabric surface when rubbed. It is possible to prevent this. Furthermore, we speculate that the polysaccharide coating is highly water resistant and has improved wet rub fastness when rubbed with a damp cloth.

Polysaccharides with amino groups include cationic cellulose, cationic starch, cationic guar gum, cationic locust bean gum, cationic fenugreek gum, cationic tara gum, cationic curdlan, cationic carrageenan, hyaluronic acid, and chondroitin sulfate. , heparin, keratan sulfate, chitin, chitosan, and chitosan derivatives. From the viewpoint of miscibility with organic acids, those with an amine value of 1 to 50 mmol/g are preferred, and those with an amine value of 5 to 30 mmol/g are more preferred. The amine value can be measured according to a general method for quantifying amino groups. As a general method for quantifying amino groups, see pages 88 to 88 of "New Experimental Chemistry Course Volume 13 Organic Chemical Structure I" (published by Maruzen Co., Ltd., edited by the Chemical Society of Japan, published November 20, 1978). It can be measured by the method described on page 99 or the method described in "Colloid Titration Method" (published by Nankodo Co., Ltd., written by Ryoichi Senju, 1st edition published November 20, 1969).
Among the polysaccharides having an amino group whose amine value satisfies the above range, chitosan and chitosan derivatives are particularly preferred since the film has high water resistance. These polysaccharides may be used alone or in combination.

The content of polysaccharide in the pretreatment liquid is preferably 1% by mass or more, more preferably 3% by mass or more based on the entire pretreatment liquid. When the polysaccharide content is 1% by mass or more, it is possible to maintain the fixability of the pigment to the fabric and improve the wet rubbing fastness. Further, the content of polysaccharides in the pretreatment liquid is preferably 20% by mass or less, more preferably 12% by mass or less, based on the entire pretreatment liquid. When the polysaccharide content is 20% by mass or less, the pretreatment liquid has a low viscosity, so occurrence of coating unevenness etc. is suppressed, and a good image can be obtained.

By containing an organic acid in the pretreatment liquid, it is possible to suppress blurring of an image. In many cases, ink is adjusted to be neutral to weakly alkaline in order to prevent head corrosion and increase ink stability. By containing an organic acid in the pre-treatment liquid, the pH of the pre-treatment liquid is lowered and the surface of the fabric is made acidic with the pre-treatment liquid, which reduces the stability of the ink and prevents pigment aggregation after printing. It is thought that this makes it easier to cause image blurring and suppresses image blurring. From the viewpoint of lowering the pH of the pretreatment liquid and increasing the cohesiveness of the pigment, it is particularly preferable to contain an organic acid with a pKa of 1 to 6.

Among organic acids having a pKa of 1 to 6, it is preferable to include a carboxylic acid having 6 or less carbon atoms. Carboxylic acids having 6 or less carbon atoms have high solubility in water, can prevent separation of water and carboxylic acid during long-term storage, and can improve the stability of the pretreatment liquid. Preferred examples of carboxylic acids having 6 or less carbon atoms include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and hexanoic acid, and hydroxy acids such as lactic acid, malic acid, and citric acid. The carbon chain may be straight or branched, and may be saturated or unsaturated. Among these, hydroxy acids having 3 to 4 carbon atoms are more preferably used as they exhibit strong acidity compared to other organic acids.

The content of the organic acid in the pretreatment liquid is preferably 1% by mass or more, more preferably 2% by mass or more based on the entire pretreatment liquid. When the content of the organic acid is 1% by mass or more, pigment aggregation can be caused and image bleeding can be suppressed. Further, the content of the organic acid in the pretreatment liquid is preferably 50% by mass or less, more preferably 15% by mass or less, based on the entire pretreatment liquid. When the content of the organic acid is 50% by mass or less, the effect of leaving the pigment on the fabric surface does not become too high, and the wet rubbing fastness can be maintained.

Moreover, it is thought that the following effects can be obtained by containing both a polysaccharide having an amino group and an organic acid. First, since the pretreatment liquid contains an organic acid, the solubility of the polysaccharide having an amino group, which is easily dissolved in an acidic aqueous solution, increases, and the stability of the pretreatment liquid can be improved. Furthermore, since the rate of pigment aggregation caused by organic acids is faster than the rate at which polysaccharides having amino groups form a film, the polysaccharide forms a film after the pigments are agglomerated by the organic acid. This further suppresses image bleeding and makes it possible to obtain printed matter with excellent wet abrasion fastness.

The pretreatment liquid may contain a surfactant. As the surfactant, one or more surfactants similar to those that can be used in the ink described below can be selected and used. The amount of surfactant in the pretreatment liquid is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount of the pretreatment liquid. The amount of surfactant in the pretreatment liquid is preferably 30% by mass or less, preferably 20% by mass or less, and preferably 10% by mass or less, based on the total amount of the pretreatment liquid.

The water contained in the pretreatment liquid is not particularly limited, but preferably contains no impurities. Examples include ion-exchanged water, distilled water, ultrapure water, and the like. The total amount of water contained in the pretreatment liquid is preferably 20% to 90% by weight, more preferably 50% to 80% by weight, based on the total amount of the pretreatment liquid.

The pretreatment liquid may contain other components such as a water-soluble organic solvent, a water-dispersible resin, an antifoaming agent, a pH adjuster, an antioxidant, and a preservative, within a range that does not impair the effects of the present invention. Good too.

The method for producing the pretreatment liquid is not particularly limited, and can be appropriately produced by any known method. For example, it can be prepared by adding all the components at once or in portions to a known stirrer, stirring, and, if desired, passing through a known filter such as a membrane filter.

[Inkjet textile ink set] The ink set of the embodiment is an inkjet textile ink set that includes a textile pretreatment liquid and an inkjet textile ink containing a pigment and water. As the textile printing pretreatment liquid, the above-mentioned textile printing pretreatment liquid can be used. According to this ink set, it is possible to suppress bleeding of an image of a printed material and to obtain a printed material with high wet rubbing fastness.

The ink for inkjet textile printing preferably contains a pigment and water.

As the pigment, any pigment commonly used in the technical field can be used. One type of pigment may be used alone, or two or more types may be used in combination. The amount of the pigment to be blended varies depending on the type of pigment used, but from the viewpoint of color development etc., it is preferably contained in the ink in an amount of about 0.1 to 30% by mass based on the total amount of the ink, and 0.1 More preferably, it is 15% by mass.

Non-white pigments include organic pigments such as azo, phthalocyanine, dye, fused polycyclic, nitro, and nitroso pigments (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, metal oxides and sulfides, as well as ocher, ultramarine, Inorganic pigments such as navy blue, carbon blacks such as furnace carbon black, lamp black, acetylene black, and channel black can be used. The average particle diameter of these pigments is preferably 50 nm or more from the viewpoint of color development, and preferably 500 nm or less from the viewpoint of ejection stability. The average particle size of these pigments is, for example, preferably 50 to 500 nm, more preferably 50 to 200 nm.

Examples of the white pigment include inorganic pigments such as titanium oxide, zinc white, zinc sulfide, antimony oxide, and zirconium oxide. In addition to inorganic pigments, hollow resin particles and polymer particles can also be used. Among them, from the viewpoint of hiding power, it is preferable to use titanium oxide.The average particle size of titanium oxide is preferably 50 nm or more from the viewpoint of hiding power, and preferably 500 nm or less from the viewpoint of ejection stability. . When using titanium oxide, it is preferable to use one whose surface has been treated with alumina or silica in order to suppress photocatalytic action. The surface treatment amount is preferably about 5 to 20% by mass in the pigment.

In order to stably disperse the pigment in the ink, it is preferable to use a pigment dispersant such as a polymer dispersant or a surfactant type dispersant. Examples of commercially available polymer dispersants include the TEGO Disperse series manufactured by EVONIK (TEGO Disperse 740W, TEGO Disperse 750W, TEGO Disperse 755W, TEGO Disperse 757W, TEGO Disperse 760W), and Japan Lubrizol. Solsperse series (Solsperse 20000, Solsperse 27000, Solsperse 41000, Solsperse 41090, Solsperse 43000, Solsperse 44000, Solsperse 46000) manufactured by Johnson Polymer Co., Ltd., Jonkryl series (Jonkryl 57, Jonkryl 60, Jonkryl 62) manufactured by Johnson Polymer Co., Ltd. , Jonkryl 63, Jonkryl 71, Jonkryl 501), DISPERBYK-102, DISPERBYK-185, DISPERBYK-190, DISPERBYK-193, DISPERBYK-199 manufactured by Big Chemie Japan Co., Ltd., polyvinyl manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Examples include pyrrolidone K-30 and polyvinylpyrrolidone K-90. Examples of surfactant-type dispersants include anionic surfactants such as the Demol series (Demol EP, Demol N, Demol RN, Demol NL, Demol RNL, Demol T-45) manufactured by Kao Corporation; Examples include nonionic surfactants such as the Emulgen series (Emulgen A-60, Emulgen A-90, Emulgen A-500, Emulgen B-40, Emulgen L-40, Emulgen 420) manufactured by Manufacturer.

These pigment dispersants can also be used in combination.
When using a pigment dispersant, the amount blended in the ink varies depending on the type and is not particularly limited, but generally the mass ratio of the active ingredient (solid content) is 0.005 to 0.5 to 1 pigment. It is preferable to use the range.

A self-dispersing pigment whose pigment surface is modified with a hydrophilic functional group may also be used. Commercially available self-dispersing pigments include, for example, the CAB-O-JET series manufactured by Cabot (CAB-O-JET200, CAB-O-JET300, CAB-O-JET250C, CAB-O-JET260M, CAB-O-JET270). ), BONJET BLACK CW-1S, CW-2, CW-3 manufactured by Orient Chemical Co., Ltd., etc.
Microencapsulated pigments in which pigments are coated with resin may also be used.

Preferably, the ink primarily contains water as the aqueous solvent. The water is not particularly limited, but preferably contains as little ionic components as possible. In particular, from the viewpoint of storage stability of the ink, it is preferable that the content of polyvalent metal ions such as calcium is low. Examples of water include ion-exchanged water, distilled water, and ultrapure water. From the viewpoint of viscosity adjustment, water is preferably contained in the ink in an amount of 20% to 80% by weight, more preferably 30% to 70% by weight, based on the total amount of the ink.

Preferably, the ink contains a water-soluble organic solvent.
The water-soluble organic solvent is preferably a water-soluble organic solvent that is liquid at room temperature and soluble in water from the viewpoint of viscosity adjustment and moisturizing effect. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1,3-propanediol, 1,3-butanediol, 1,2-butanediol, 1, Lower alcohols such as 2-pentanediol, 1,2-hexanediol, 2-methyl-2-propanol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, Glycols such as propylene glycol and butylene glycol; Glycerins such as glycerin and diglycerin; Acetins (monoacetin, diacetin, triacetin); diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, triethylene glycol monohexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene Derivatives of glycols such as glycol monobutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether; triethanolamine, 2- Pyrrolidone, 1-methyl-2-pyrrolidone, β-thiodiglycol, sulfolane, methyl ethyl ketone, ethyl acetate, etc. can be used. Polyethylene glycol with an average molecular weight in the range of 190 to 630, such as an average molecular weight of 200, 300, 400, 600, diol type polypropylene glycol, with an average molecular weight in the range of 200 to 600, such as an average molecular weight of 400, etc. It is also possible to use low molecular weight polyalkylene glycols such as triol type polypropylene glycols having an average molecular weight in the range of 250 to 800.

These water-soluble organic solvents can be used alone or in combination of two or more. From the viewpoint of viscosity adjustment and moisturizing effect, the water-soluble solvent is preferably contained in the ink in an amount of 1 to 80% by mass, more preferably 1 to 60% by mass, based on the total amount of the ink. For example, , 1 to 50% by weight, and 5 to 40% by weight.

Preferably, the ink contains a water-dispersible resin. A water-dispersible resin is one that can be dispersed in the form of particles without being dissolved in water to form an oil-in-water (O/W) emulsion. It is thought that by adding a water-dispersible resin to the ink, the adhesive strength between the fabric and the ink can be further improved. Furthermore, water-dispersible resins are insoluble in water, and the resulting film tends to have high water resistance. It is thought that these make it possible to further improve the wet rubbing fastness.

Examples of water-dispersible resins include water-dispersible urethane resins, water-dispersible acrylic resins, water-dispersible vinyl acetate resins, water-dispersible styrene/(meth)acrylic resins, water-dispersible vinyl chloride resins, and water-dispersible polyamides. Examples include resins, and these can be used alone or in combination of two or more. The water-dispersible resin may be anionic, cationic, or nonionic, with anionic water-dispersible resins being preferred.

The amount of water-dispersible resin in the ink is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total amount of the ink. Further, the amount of water-dispersible resin in the ink is preferably 20% by mass or less, and preferably 10% by mass or less, based on the total amount of the ink.

The ink may contain other components as appropriate. Other components include surface tension modifiers (surfactants), antioxidants, preservatives, crosslinking agents, and the like.

As the surface tension adjusting agent, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, or polymeric, silicone, or fluorine-based surfactants can be used.

By blending this surfactant, it becomes easier to eject ink stably by an inkjet method, and the permeation of the ink can be easily controlled, which is preferable. The amount added (if a surfactant is used as a pigment dispersant, the total amount) varies depending on the type of surfactant, but it depends on the surface tension of the ink and the rate of penetration into the base material such as fabric. From this point of view, it is preferable that the amount in the ink is in the range of 0.1 to 10% by mass.

Specifically, the anionic surfactants include Kao Corporation's Emar series (Emar 0, Emar 10, Emar 2F, Emar 40, Emar 20C), Neoperex series (Neoperex GS, Neoperex G-15, Neoperex G-25, Neoperex G-65), Perex series (Perex OT-P, Perex TR, Perex CS, Perex TA, Perex SS-L, Perex SS-H), Demol series (Demol N, Demol NL) , Demol RN, Demol MS). Examples of cationic surfactants include the Kao Corporation's Acetamine series (Acetamine 24, Acetamine 86), Cortamine series (Cortamine 24P, Cortamine 86P, Cortamine 60W, Cortamine 86W), and Sanizol series (Sanizol C, Sanizol). B-50).

Examples of nonionic surfactants include the Surfynol series manufactured by Air Products (Surfynol 104E, Surfynol 104H, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485) and Nissin Chemical Co., Ltd. Acetylene glycol surfactants such as Olfine E1004, Olfine E1010, Olfine E1020, and the Emulgen series manufactured by Kao Corporation (Emulgen 102KG, Emulgen 103, Emulgen 104P, Emulgen 105, Emulgen 106, Emulgen 108, Emulgen 120, Emulgen 147, Emulgen) 150, Emulgen 220, Emulgen 350, Emulgen 404, Emulgen 420, Emulgen 705, Emulgen 707, Emulgen 709, Emulgen 1108, Emulgen 4085, Emulgen 2025G).

Examples of the amphoteric surfactant include the Anhitol series manufactured by Kao Corporation (Amhitol 20BS, Amhitol 24B, Amhitol 86B, Amhitol 20YB, Amhitol 20N), and the like.

The viscosity of the ink can be adjusted as appropriate, but for example, from the viewpoint of ejection properties, the viscosity at 23° C. is preferably 1 to 30 mPa·s.

The method for manufacturing the ink is not particularly limited, and the ink can be appropriately manufactured by any known method. For example, it can be prepared by charging all the components at once or in portions into a known stirrer or disperser, stirring or dispersing them, and, if desired, passing them through a known filter such as a membrane filter.

The ink jet recording method may be any method such as a piezo method, an electrostatic method, or a thermal method.

[Method for producing a printed article] The method for producing a printed article according to the embodiment includes a step of applying a pre-treatment liquid for printing to a fabric (hereinafter sometimes referred to as "Step 1"), and a step in which the pre-treatment liquid is applied. The method includes a step of forming an image on a fabric by an inkjet recording method using an inkjet printing ink containing a pigment and water (hereinafter sometimes referred to as "step 2"). As for the textile printing pretreatment liquid, the above-mentioned textile printing pretreatment liquid can be used. Regarding the inkjet textile printing inks, those described as those that can be used together with the above-mentioned textile printing pretreatment liquid can be used. According to this method for producing a printed product, bleeding of the image of the printed product is suppressed, and it is possible to obtain a printed product with high wet rubbing fastness.

In step 1, the pretreatment liquid is preferably applied to at least the area of the fabric where an image will be formed in step 2 (hereinafter sometimes referred to as "printing area"), and is preferably applied to the entire surface of the fabric including the printing area. You may. Application of the pretreatment liquid in Step 1 is not particularly limited, and can be performed, for example, by a padding method, a coating method, a screen printing method, an inkjet method, a spray method, or the like. It is preferable to print by an inkjet method because it is easy to control the amount of pretreatment liquid applied when it is small. When applying the pretreatment liquid to the entire surface of the substrate, application by spraying or roller is preferred from the viewpoint of productivity. The amount of the pretreatment liquid applied to the fabric may be, for example, 0.5 to 200 g/m ² or 1 to 20 g/m ² . Further, the amount of the pretreatment liquid applied to the fabric may be, for example, 0.1 to 120% by mass, or 1 to 60% by mass, based on the mass of the fabric.

In step 2, an image can be formed on the fabric by scanning the inkjet head over the fabric and applying ink to desired positions. Known inkjet recording methods and devices can be used. The inkjet recording device used may be of any type, such as a piezo system, an electrostatic system, or a thermal system. For example, ink droplets are ejected from an inkjet head based on digital signals, and Depositing an ink droplet onto a substrate. An image may be formed by applying a plurality of types of ink.

Examples of commercially available inkjet recording devices include EPSON SC-F2150 manufactured by Seiko Epson Corporation, Tx300P-1800 and Tx300P-1800B manufactured by Mimaki Engineering Co., Ltd., FUJIFILM DM-2850 manufactured by Fuji Film Corporation, and FUJIFILM DM-2850 manufactured by Mastermind Corporation. Examples include, but are not limited to, MMP-8130.

Fabric is preferably used as the base material. As the fabric, for example, a fabric made of any natural or synthetic fiber such as cotton, silk, wool, hemp, nylon, polyester, rayon, acetate, cupro, etc. can be used. Examples of the fabric include woven fabrics, knitted fabrics, and nonwoven fabrics. Further, the base material may be, for example, a colored base material. For example, the substrate may be black or dark colored.

The amount of ink applied to the fabric is not particularly limited, but from the viewpoint of texture, it is preferably 500 g/m ² or less, more preferably 100 g/m 2 or less, and 50 g/m ² or less per unit area of the fabric. More preferably, it is ² or less.

The method for producing a printed article may further include a heating step of heat-treating the fabric. For example, after step 1 and/or after step 2, a heating step may be performed to heat-treat the fabric. By performing the heat treatment, the resin can be fused to the surface of the fabric, and the water contained in the ink and pretreatment liquid can be evaporated. By performing the heating step, images with better printing durability tend to be obtained. The heat treatment method is not particularly limited, and examples thereof include heating on a hot plate, heat press method, normal pressure steam method, high pressure steam method, and thermofix method. The temperature during the heat treatment may be, for example, as long as it can fuse the resin and evaporate water, and is preferably 100°C to 220°C, more preferably about 120°C to 180°C.

However, with the pretreatment liquid of the present invention, it is possible to suppress image bleeding and obtain printed matter with high wet rubbing fastness even without heat treatment after step 1. From the viewpoint of productivity, it is preferable not to include a heating step after step 1, and after applying the pretreatment liquid to the fabric, printing is performed while the fabric is wet with the pretreatment liquid without going through the heating process. It is preferable. By printing within 45 seconds in an environment of 50° C. or lower after applying the pretreatment liquid, it is possible to print before the pretreatment liquid dries.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples. Note that the amount of each component is not the solid content (active ingredient) equivalent amount, but the amount of each product.

[Preparation of pre-treatment liquid] The materials listed in Tables 1 to 3 were mixed, thoroughly stirred using a Three-One Motor (manufactured by Shinto Kagaku Co., Ltd.), and then filtered through a membrane filter with a pore size of 0.8 μm. Coarse particles were removed to prepare pretreatment liquids for Examples 1 to 16 and Comparative Examples 1 to 6. The materials listed in Tables 1 to 3 are as follows. Furthermore, numerical values without units for each component indicate mass %.

<Polysaccharide>・Cationized cellulose: MERQUAT 2003PR (manufactured by Japan Lubrizol Co., Ltd.)・Cationized starch: SENSOMER Cl-50 (manufactured by Japan Lubrizol Co., Ltd.)・Chitosan: Glycol chitosan (Fujifilm Wako Pure Chemical Industries, Ltd.) Chitosan: Chitosan 10 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Cationized guar gum: Mayprobond 111 (manufactured by Sansho Co., Ltd.) <Organic acid> Acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ), hexanoic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), sorbic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), lactic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), malic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (Manufactured by Yaku Kogyo Co., Ltd.) Citric acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) <Surfactant> Sylface SAG503A (manufactured by Nissin Chemical Industry Co., Ltd.): Polyether-modified silicone surfactant <Ion exchange Water＞・Ion exchange water

[Preparation of pigment dispersion] 20 parts of carbon black MA-230 (C.I. Pigment Black 7, manufactured by Mitsubishi Chemical Corporation), Joncryl 61J (manufactured by Johnson Polymer Co., Ltd., polymer dispersant, active ingredient 30.5%) ), 10 parts of Surfynol GA (manufactured by Nissin Chemical Industry Co., Ltd., nonionic surfactant, active ingredient 85%), and 50 parts of ion exchange water were mixed, and the mixture was mixed with an ultrasonic homogenizer "Ultrasonic processor VC-750". (manufactured by Sonics) for 10 minutes under vibration conditions of approximately 13 MPa to produce a pigment dispersion.

11 parts of the prepared pigment dispersion, 10 parts of Superflex 860 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane water-dispersible resin (anionic: solid content concentration 40%)), Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) , nonionic surfactant), 20 parts of glycerin (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 53 parts of ion-exchanged water, and thoroughly mixed using a Three-One Motor (manufactured by Shinto Kagaku Co., Ltd.). After stirring, the mixture was filtered through a membrane filter with a pore size of 0.8 μm to remove coarse particles, thereby obtaining an inkjet textile ink.

[Evaluation] <Preparation of printed matter (printed material)> A test piece was prepared by cutting 100% cotton oxford cloth into a size of 250 mm x 100 mm, and a pretreatment liquid was applied by spraying. The amount of pretreatment liquid applied was 6.5 g/m ² . The prepared ink was introduced into an inkjet printer (textile printer "MMP-8130" manufactured by Mastermind), and 30 seconds after the pretreatment liquid was applied, the following image was printed. After printing, it was heated at 150° C. for 60 seconds using a HotronixFusion heat press (manufactured by Stahls Hotronix).

<Image bleeding evaluation method> Printed materials with the word "new" printed in font sizes of 12 pt and 16 pt were visually checked to evaluate image bleeding. The results are shown in Tables 1 to 3. A: There is no bleeding in both 12pt and 16pt characters and they are legible. B: I can't read 12pt characters, but I can read 16pt characters. C: Bleeding is observed in both 12pt and 16pt characters, making them difficult to read.

<Wet rubbing fastness evaluation method> A 220 mm x 75 mm black solid image was printed as a test piece so that the ink transfer amount was 20 g/ ^m2 , and the wet rubbing fastness of the test piece was evaluated based on JIS L 0849. evaluated. Using a Gakushin tester RT-200 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), the surface was rubbed 100 times without a weight, and contamination was evaluated on a gray scale. The attached fabric was 100% cotton Kanakin No. 3, and was used after being moistened with ion-exchanged water of the same mass as the fabric. Evaluation was made using the following evaluation criteria. A: Grade 3 or higher B: Grade 2 or higher but less than grade 3 C: Grade 1-2 or lower

In Examples 1 to 16, in which a pretreatment liquid containing 1 to 20% by mass of a polysaccharide having an amino group and 1 to 50% by mass of an organic acid, and an inkjet ink containing at least a pigment and water, "Image Good results were obtained in both the evaluation items of ``bleeding'' and ``wet rubbing fastness'', indicating that it is possible to suppress image bleeding and produce printed printed matter with high wet rubbing fastness. Ta. Examples 3, 4, 6 to 11, in which the polysaccharide was chitosan and chitosan derivatives, showed better results in terms of wet rub fastness. Further, in Examples 1 to 5, 9, and 11 to 14, in which the organic acid was a hydroxy acid having 3 to 4 carbon atoms, better results were obtained in terms of image blur.

On the other hand, in Comparative Example 1, which did not contain a pretreatment liquid, Comparative Example 3, which did not contain a polysaccharide in the pretreatment liquid, and Comparative Example 4, in which the amount of organic acid exceeded 50% by mass, the wet rubbing fastness was poor. . In addition, in Comparative Example 2 in which the pretreatment liquid does not contain an organic acid, Comparative Example 5 in which the pretreatment liquid has a low organic acid content, and Comparative Example 6 in which the pretreatment liquid contains more than 20% by mass of polysaccharides, the image The bleeding results were poor.

Claims (5)

A pretreatment liquid used with an inkjet ink containing at least a pigment and water, the pretreatment liquid containing 3 to 12 % by mass of a polysaccharide having an amino group and 2 to 50% by mass of an organic acid , 1. A pretreatment liquid for textile printing, characterized in that the polysaccharide having an amino group is at least one selected from chitosan and chitosan derivatives . The printing pretreatment liquid according to claim 1, wherein the organic acid is a carboxylic acid having 1 to 6 carbon atoms. The printing pretreatment liquid according to claim 2 , wherein the carboxylic acid is a hydroxy acid having 3 to 4 carbon atoms. An image is recorded on a fabric by applying the textile pretreatment liquid according to any one of claims 1 to 3 and ejecting ink containing at least a pigment and water from an inkjet head. Method of manufacturing printed materials. An inkjet textile ink set comprising the textile pretreatment liquid according to any one of claims 1 to 3 and an inkjet textile ink containing a pigment and water.